KR20230169195A - Curable organopolysiloxane composition, thermally conductive member and heat dissipation structure - Google Patents
Curable organopolysiloxane composition, thermally conductive member and heat dissipation structure Download PDFInfo
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- KR20230169195A KR20230169195A KR1020237037867A KR20237037867A KR20230169195A KR 20230169195 A KR20230169195 A KR 20230169195A KR 1020237037867 A KR1020237037867 A KR 1020237037867A KR 20237037867 A KR20237037867 A KR 20237037867A KR 20230169195 A KR20230169195 A KR 20230169195A
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- 239000000203 mixture Substances 0.000 title claims abstract description 187
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 125
- 230000017525 heat dissipation Effects 0.000 title claims abstract description 56
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- 239000000194 fatty acid Substances 0.000 claims abstract description 45
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- 150000004665 fatty acids Chemical class 0.000 claims abstract description 34
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- 239000002184 metal Substances 0.000 claims abstract description 22
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- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- NRYWFNLVRORSCA-UHFFFAOYSA-N triethoxy(6-triethoxysilylhexyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCC[Si](OCC)(OCC)OCC NRYWFNLVRORSCA-UHFFFAOYSA-N 0.000 description 1
- OXQUKGVMOJFCGS-UHFFFAOYSA-N trimethoxy(5-trimethoxysilylhexan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)CCC(C)[Si](OC)(OC)OC OXQUKGVMOJFCGS-UHFFFAOYSA-N 0.000 description 1
- ODWVKKAQQWZKHG-UHFFFAOYSA-N trimethoxy(6-trimethoxysilylhexan-2-yl)silane Chemical compound CO[Si](OC)(OC)CCCCC(C)[Si](OC)(OC)OC ODWVKKAQQWZKHG-UHFFFAOYSA-N 0.000 description 1
- BHXFSPFDYQBPQY-UHFFFAOYSA-N trimethoxy(6-trimethoxysilylhexan-3-yl)silane Chemical compound CO[Si](OC)(OC)C(CC)CCC[Si](OC)(OC)OC BHXFSPFDYQBPQY-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
[과제] 높은 열전도율을 가지면서, 가열 에이징 후에도 경화물의 경도 변화가 억제되고 있으며, 당해 경화물로 이루어진 열전도성 부재를 고온하에서 사용한 경우에도 유연성 및 응력 완화 특성을 유지할 수 있는 오가노폴리실록산 경화물을 부여하는 경화성 오가노폴리실록산 조성물, 이것으로 이루어진 열전도성 부재 및 이를 이용하는 방열 구조체를 제공한다. [해결 수단] (A) 특정 점도의 알케닐기 함유 오가노폴리실록산, (B) 오가노하이드로겐폴리실록산, (C) 열전도성 충전제, 조성물 중의 고형분 전체에 대하여 60~90 부피%의 범위가 되는 양, (D) 지방산, 지방산 에스테르 및 지방산 금속염으로부터 선택되는 적어도 1종류 이상 성분, (C) 100 질량부에 대하여 0.05~2.00 질량부가 되는 범위의 양, (E) 촉매량의 하이드로실릴화 반응용 촉매, (F) 내열성 부여제를 함유하는, 경화성 오가노폴리실록산 조성물 및 그의 사용.[Project] A cured organopolysiloxane that has high thermal conductivity, suppresses changes in hardness of the cured product even after heat aging, and maintains flexibility and stress relief properties even when a thermally conductive member made of the cured product is used at high temperatures. Provided is a curable organopolysiloxane composition, a heat conductive member made of the same, and a heat dissipation structure using the same. [Solution] (A) alkenyl group-containing organopolysiloxane of a specific viscosity, (B) organohydrogenpolysiloxane, (C) thermally conductive filler, in an amount ranging from 60 to 90% by volume based on the total solid content in the composition, (D) at least one component selected from fatty acids, fatty acid esters, and fatty acid metal salts, (C) an amount in the range of 0.05 to 2.00 parts by mass per 100 parts by mass, (E) a catalytic amount of a catalyst for hydrosilylation reaction, ( F) Curable organopolysiloxane composition containing heat resistance imparting agent and use thereof.
Description
본 발명은 높은 열전도율을 가지면서, 가열 에이징 후에도 경화물의 경도 변화가 억제되고 있고, 당해 경화물로 이루어진 열전도성 부재를 고온하에서 사용한 경우에도 유연성 및 응력 완화 특성을 유지할 수 있는 오가노폴리실록산 경화물을 부여하는 경화성 오가노폴리실록산 조성물, 이것으로 이루어진 열전도성 부재 및 이를 사용하는 방열 구조체에 관한 것이다.The present invention provides a cured organopolysiloxane that has high thermal conductivity, suppresses changes in hardness of the cured product even after heat aging, and maintains flexibility and stress relief properties even when a thermally conductive member made of the cured product is used at high temperatures. It relates to a curable organopolysiloxane composition, a heat conductive member made of the same, and a heat dissipation structure using the same.
최근, 트랜지스터, IC, 메모리 소자 등의 전자 부품을 등재한 프린트 회로 기판이나 하이브리드 IC의 고밀도·고집적화, 이차전지(셀식)의 용량 증대에 따라, 전자 부품이나 전지 등의 전자·전기 기기로부터 발생하는 열을 효율적으로 방열하기 위해, 오가노폴리실록산, 및 산화알루미늄 분말, 산화아연 분말 등의 열전도성 충전제로 이루어진 열전도성 실리콘 조성물이 널리 이용되고 있으며, 특히 높은 방열량에 대응하기 위해, 다량의 열전도성 충전제를 충전한 열전도성 실리콘 조성물이 제안되고 있다. 열전도성 실리콘 조성물은 내열성이 우수하고, 또한 열전도성 충전제를 고농도 및 고 부피%로 배합해도 그 경화물이 고무상이기 때문에, 일정한 유연성과 응력 완화성을 가지며, 방열 구조체에서의 열원에 대한 추종성과 밀착성을 유지하여, 방열 성능을 유지할 수 있는 것이 기대된다. 한편, 최근에는 열전도성 충전제의 고배합이 요구되는 경향이 있는데, 일반적으로 고분자 실리콘 경화물 유래의 고무 물성은 열전도성 충전제를 다량으로 배합하면 손상되는 경향이 있으며, 열전도성 충전제의 함유량이 너무 많으면, 얻어지는 경화물이 너무 단단해져, 방열 대상과의 간극을 발생시키거나 하여 추종성이나 응력 완화성이 손상되고, 오히려 충분한 방열성을 실현할 수 없게 되는 경우가 있다. 즉, 경화성의 열전도성 실리콘 조성물에 있어서, 그의 열전 전도성 경화물의 경도를 컨트롤하는 것은 방열성의 실현상, 지극히 중요한 과제이다.Recently, with the increase in density and integration of printed circuit boards and hybrid ICs containing electronic components such as transistors, ICs, and memory elements, and the increase in capacity of secondary batteries (cell type), the emissions from electronic and electrical devices such as electronic components and batteries have increased. In order to efficiently dissipate heat, thermally conductive silicone compositions consisting of organopolysiloxane and thermally conductive fillers such as aluminum oxide powder and zinc oxide powder are widely used. In particular, to cope with high heat dissipation, a large amount of thermally conductive fillers are used. A thermally conductive silicone composition filled with has been proposed. The thermally conductive silicone composition has excellent heat resistance, and even if the thermally conductive filler is mixed at a high concentration and high volume %, the cured product is in a rubber state, so it has certain flexibility and stress relief properties, and has excellent followability to the heat source in the heat dissipation structure. It is expected that adhesion can be maintained and heat dissipation performance can be maintained. Meanwhile, recently, there has been a trend to require a high blending of thermally conductive fillers. In general, the properties of rubber derived from cured polymer silicone tend to be damaged when a large amount of thermally conductive filler is blended, and when the content of thermally conductive filler is too high, the physical properties of rubber derived from cured polymer silicone tend to be damaged. In some cases, the resulting cured product becomes too hard, creating a gap with the heat dissipation object, impairing followability and stress relaxation, and making it impossible to achieve sufficient heat dissipation. That is, in curable thermally conductive silicone compositions, controlling the hardness of the thermoelectrically conductive cured product is an extremely important task in terms of realizing heat dissipation properties.
한편, 특허문헌 1에는 질화붕소 분말을 포함하는 실리콘계의 절연 방열 시트용 조성물에 있어서, 스테아르산 화합물을 흡습 도전의 방지제 및 이형성 개선의 목적으로 한정된 양 첨가하는 것이 제안되어 있다. 그러나, 특허문헌 1에는, 오가노폴리실록산 100 중량부에 대하여 500 중량부를 초과하는, 열전도성 충전제를 높은 부피%로 포함하는 고방열성의 조성물은 조금도 개시되어 있지 않다. 또한, 특허문헌 1에는, 스테아르산 화합물을 열전도성 충전제를 고충전한 경화물에 대하여 사용한 경우, 그의 경도에 미치는 영향에 대해 어떠한 기재도 시사도 되어 있지 않으며, 열전 전도성 경화물의 경도를 컨트롤한다는 과제 및 해결 수단을 부여하는 것이 아니다.On the other hand, Patent Document 1 proposes adding a limited amount of a stearic acid compound to a composition for a silicon-based insulating heat dissipation sheet containing boron nitride powder for the purpose of preventing moisture absorption and conduction and improving release properties. However, Patent Document 1 does not disclose any composition with high heat dissipation properties containing a high volume % of a thermally conductive filler, exceeding 500 parts by weight based on 100 parts by weight of organopolysiloxane. In addition, in Patent Document 1, when a stearic acid compound is used for a cured product highly filled with a thermally conductive filler, there is no description or suggestion regarding the effect on the hardness thereof, and the problem of controlling the hardness of the thermoelectrically conductive cured product and It does not provide a means of solution.
또한, 특허문헌 2에는, 스테아르산 철 등의 카복실산의 금속염을 포함하는, 촉매량의 축합 촉매를 사용하는 도전성 실리콘 접착제가 제안되어 있다. 그러나, 특허문헌 2에는, 하이드로실릴화 반응 경화성의 조성물은 조금도 기재도 시사도 되어 있지 않으며, 열전도성 충전제를 높은 부피%로 포함하는 고방열성의 조성물은 조금도 개시되어 있지 않다. 또한, 특허문헌 2에는, 스테아르산 철 등은 어디까지나 축합 촉매로서, 당해 성분을 하이드로실릴화 반응 경화성의 조성물이며, 열전도성 충전제를 고충전한 경화물에 대하여 사용한 경우, 그의 경도에 미치는 영향에 대해 어떠한 기재도 시사도 되어 있지 않으며, 열전 전도성 경화물의 경도를 컨트롤한다는 과제 및 해결 수단을 부여하는 것이 아니다.Additionally, Patent Document 2 proposes a conductive silicone adhesive that uses a catalytic amount of a condensation catalyst containing a metal salt of carboxylic acid such as iron stearate. However, in Patent Document 2, no description or suggestion is made of a hydrosilylation reaction-curable composition, and no composition of high heat dissipation property containing a high volume % of a thermally conductive filler is disclosed at all. In addition, Patent Document 2 describes the effect on hardness of iron stearate, etc., as a condensation catalyst, when the component is used in a cured product highly charged with a heat conductive filler in a hydrosilylation reaction curable composition. No description or suggestion is made, and the problem and means of solving the problem of controlling the hardness of the thermoelectrically conductive cured product are not given.
마찬가지로 특허문헌 3에는, 전기 전도성의 경화 실리콘 생성물이 제안되어 있다. 그러나, 특허문헌 3에는, 하이드로실릴화 반응 경화성의 조성물은 어떠한 기재도 시사도 되어 있지 않으며, 열전도성 충전제를 높은 부피%로 포함하는 고방열성의 조성물은 조금도 개시되어 있지 않다. 또한, 특허문헌 3에서, 플레이크 형태의 금속 입자 표면을 지방산 또는 지방산 에스테르로 처리할 수도 있다는 취지가 기재되어 있지만, 그의 처리량이나 하이드로실릴화 반응 경화성 조성물에 적용한 경우의 효과 등은 하등 기재도 시사도 되어 있지 않으며, 지방산의 기재는 일반적인 분체 표면 처리 범위에 그쳐, 그의 기술적 효과, 특히 하이드로실릴화 반응 경화성의 조성물로서, 열전도성 충전제를 고충전한 경화물에 대해 사용한 경우, 그 경도에 미치는 영향에 대해 조금도 기재도 시사도 되어 있지 않다.Similarly, Patent Document 3 proposes an electrically conductive cured silicone product. However, in Patent Document 3, there is no description or suggestion of a composition curable by hydrosilylation reaction, and no composition with high heat dissipation property containing a high volume % of a heat conductive filler is disclosed at all. In addition, in Patent Document 3, it is stated that the surface of flake-shaped metal particles can be treated with fatty acid or fatty acid ester, but the amount of treatment or the effect when applied to the hydrosilylation reaction curable composition is not described or suggested at all. The description of fatty acids is limited to the scope of general powder surface treatment, and its technical effects, especially its effect on hardness when used on a hydrosilylation reaction curable composition highly filled with a thermally conductive filler, are discussed. There is no description or suggestion whatsoever.
아울러, 상기 어느 문헌에도, 하이드로실릴화 반응 경화성의 실리콘 조성물에 있어서, 지방산 등을 프탈로시아닌 화합물 등의 내열성 부여제와 병용하는 것에 대해, 어떠한 기재도 시사도 되어 있지 않다.Additionally, none of the above-mentioned documents describes or suggests the use of fatty acids and the like in combination with a heat resistance imparting agent such as a phthalocyanine compound in a hydrosilylation reaction-curable silicone composition.
한편, 본건 발명자들은 하이드로실릴화 반응 경화성의 열전도성 실리콘 조성물에 있어서, 새로운 과제를 발견했다. 상기와 같이, 열전도성 충전제를 다량으로 배합한 열전도성 실리콘 조성물을 경화시키면, 경화물이 단단해지기 쉽고, 높은 열전도율과 경화물의 유연성은 트레이드 오프의 관계에 있는 경우가 많다. 그러나, 경화물의 경도와 열전도율을 조절하여 열전도성 실리콘 조성물을 설계한 경우이더라도, 상기와 같은 열전도성 충전제를 매우 높은 부피%(예를 들어, 조성물 전체(고형분)에 대하여 60 부피% 이상)로 포함하는 고방열성의 조성물의 경우, 경화물이 가열 에이징 후에 급격하게 단단해져 유연성 및 고무 탄성을 잃고, 응력 완화성이나 방열 구조에서의 추종성, 밀착성이 손상되는 경우가 있다. 이에 수반하여, 본래 예정하고 있는 방열 특성을 충분히 실현할 수 없게 되는 경우가 있다.Meanwhile, the present inventors discovered a new problem in the hydrosilylation reaction-curable thermally conductive silicone composition. As described above, when a thermally conductive silicone composition containing a large amount of thermally conductive filler is cured, the cured product tends to become hard, and there is often a trade-off between high thermal conductivity and flexibility of the cured product. However, even if the thermally conductive silicone composition is designed by controlling the hardness and thermal conductivity of the cured product, the thermally conductive filler as described above is included in a very high volume% (e.g., 60% by volume or more based on the entire composition (solid content)). In the case of a composition with high heat dissipation properties, the cured product hardens rapidly after heat aging, loses flexibility and rubber elasticity, and may lose stress relaxation properties, followability in the heat dissipation structure, and adhesion. As a result, there are cases where the originally intended heat dissipation characteristics cannot be sufficiently realized.
본 발명은 상기 과제를 해결하기 위해 이루어진 것으로, 열전도성 충전제를 매우 높은 부피%로 함유하기 때문에, 높은 열전도율을 가지면서, 가열 에이징 후에도 경화물의 경도 변화가 억제되고 있으며, 당해 경화물로 이루어진 열전도성 부재를 고온하에서 사용한 경우에도 유연성 및 응력 완화 특성을 유지할 수 있는 오가노폴리실록산 경화물을 부여하는 경화성 오가노폴리실록산 조성물, 이것으로 이루어진 열전도성 부재 및 이를 이용하는 방열 구조체를 제공하는 것을 목적으로 한다.The present invention was made to solve the above problems. Since the thermally conductive filler is contained in a very high volume%, it has high thermal conductivity and the change in hardness of the cured product is suppressed even after heat aging, and the thermal conductive material made of the cured product is suppressed. The purpose of the present invention is to provide a curable organopolysiloxane composition that provides a cured organopolysiloxane that can maintain flexibility and stress relief properties even when the member is used at high temperatures, a heat conductive member made of the same, and a heat dissipation structure using the same.
예의 검토한 결과, 본 발명자들은 높은 열전도율을 부여하기 위해 열전도성 충전제를 다량(구체적으로는 조성물의 고형분 전체에 대하여 60~90 부피%가 되는 범위)으로 포함하고, 하이드로실릴화 반응 경화성의 조성물로서, 지방산, 지방산 에스테르 및 지방산 금속염으로부터 선택되는 적어도 1종류 이상의 지방산계 화합물 및 내열성 부여제를 일정량 포함하는 경화성 오가노폴리실록산 조성물에 의해 상기 과제를 해결 가능한 것을 밝혀내고, 본 발명에 도달했다. 여기서, 지방산계 화합물은 스테아르산, 스테아르산의 알칼리 금속염(리튬염 등), 스테아르산의 알칼리 토류 금속염(칼슘염 등)으로 대표되는 포화 지방산계 화합물인 것이 특히 바람직하다. 또한, 조성물을 조정하는 경우, 지방산계 화합물의 타이밍은 임의이며, 조성물의 주제(主劑)인 알케닐기 함유 오가노폴리실록산 및 열전도성 충전제와 함께 혼합하고 가열(베이스 히트)할 수도 있고, 알케닐기 함유 오가노폴리실록산 및 열전도성 충전제를 혼합하고, 베이스 히트 후의 혼합물에 그 외 성분과 함께 첨가할 수도 있다. 즉, 지방산계 화합물은 열전도성 충전제의 표면 처리제가 되는 타이밍 이외에 본 발명에 관한 조성물에 첨가해도, 본 발명의 기술적 효과는 달성된다.(실시예 참조)As a result of careful study, the present inventors have found that a large amount of thermally conductive filler (specifically, in the range of 60 to 90% by volume based on the total solid content of the composition) is included in order to provide high thermal conductivity, and that the composition is hydrosilylation reaction-curable. It was discovered that the above problems can be solved by a curable organopolysiloxane composition containing a certain amount of at least one type of fatty acid-based compound selected from fatty acids, fatty acid esters, and fatty acid metal salts and a heat resistance imparting agent, and the present invention was achieved. Here, the fatty acid-based compound is particularly preferably a saturated fatty acid-based compound represented by stearic acid, an alkali metal salt of stearic acid (lithium salt, etc.), and an alkaline earth metal salt of stearic acid (calcium salt, etc.). In addition, when adjusting the composition, the timing of the fatty acid-based compound is arbitrary, and the alkenyl group-containing organopolysiloxane and the heat conductive filler, which are the main components of the composition, may be mixed and heated (base heat). The containing organopolysiloxane and thermally conductive filler may be mixed and added together with other ingredients to the mixture after the base heat. In other words, the technical effect of the present invention is achieved even if the fatty acid-based compound is added to the composition according to the present invention at a time other than when it is used as a surface treatment agent for the thermally conductive filler (see examples).
구체적으로는, 본 발명의 목적은Specifically, the purpose of the present invention is
(A) 25℃에서의 점도가 10~100,000 mPa·s인 알케닐기 함유 오가노폴리실록산 100 질량부,(A) 100 parts by mass of an alkenyl group-containing organopolysiloxane having a viscosity of 10 to 100,000 mPa·s at 25°C,
(B) 오가노하이드로겐폴리실록산: 성분 (A)에 포함되는 알케닐기 1몰에 대하여, 성분 (B) 중의 규소 원자 결합 수소 원자가 0.1~10몰이 되는 양,(B) Organohydrogenpolysiloxane: an amount of 0.1 to 10 moles of hydrogen atoms bonded to silicon atoms in component (B) relative to 1 mole of alkenyl groups contained in component (A),
(C) 열전도성 충전제, 조성물 중의 고형분 전체에 대하여 60~90 부피%의 범위가 되는 양,(C) thermally conductive filler, in an amount ranging from 60 to 90% by volume based on the total solid content in the composition,
(D) 지방산, 지방산 에스테르 및 지방산 금속염으로부터 선택되는 적어도 1종류 이상, 성분 (C) 100 질량부에 대하여 0.05~2.00 질량부가 되는 범위의 양,(D) at least one type selected from fatty acids, fatty acid esters, and fatty acid metal salts, in an amount ranging from 0.05 to 2.00 parts by mass based on 100 parts by mass of component (C),
(E) 촉매량의 하이드로실릴화 반응용 촉매,(E) a catalytic amount of a catalyst for hydrosilylation reaction,
(F) 내열성 부여제(F) Heat resistance imparting agent
를 함유하며,Contains,
또한 임의로,Also randomly,
(G) 이하의 성분 (G1) 및 성분 (G2)로부터 선택되는 1종류 이상의 성분(G) One or more components selected from the following components (G1) and (G2)
(G1) 일반식 (1):(G1) General formula (1):
[화 1][Tuesday 1]
(식 중, R1은 독립적으로 비치환 또는 치환된 탄소-탄소 이중 결합을 갖지 않는 1가 탄화수소기이고, R2는 독립적으로 수소 원자, 알킬기, 알콕시알킬기 또는 아실기이고, a는 5~250의 정수이고, b는 1~3의 정수이다.)로 표시되고, 25℃에서의 점도가 10~10,000 mPa·s 미만인 오가노폴리실록산,(In the formula, R 1 is independently an unsubstituted or substituted monovalent hydrocarbon group without a carbon-carbon double bond, R 2 is independently a hydrogen atom, an alkyl group, an alkoxyalkyl group or an acyl group, and a is 5 to 250 is an integer, and b is an integer of 1 to 3. Organopolysiloxane represented by ) and having a viscosity of less than 10 to 10,000 mPa·s at 25°C,
(G2) 일반식 (2):(G2) General formula (2):
RalkR3 2SiO(R3 2SiO)cR3 2Si-R4-SiR3 (3-d)(OR5)d R alk R 3 2 SiO(R 3 2 SiO) c R 3 2 Si-R 4 -SiR 3 (3-d) (OR 5 ) d
(식 중, Ralk는 알케닐기이고, R3은 독립적으로 비치환 또는 치환된 탄소-탄소 이중 결합을 갖지 않는 1가 탄화수소기이고, R4는 산소 원자 또는 2가 탄화수소기이고, R5는 독립적으로 수소 원자, 알킬기, 알콕시알킬기 또는 아실기이고, c는 1~250의 정수이고, d는 1~3의 정수이다.)로 표시되고, 25℃에서의 점도가 10~10,000 mPa·s의 범위에 있는, 분자쇄 말단에 알케닐기 및 가수 분해성 실릴기를 갖는 실록산계 화합물, 및(Wherein, R alk is an alkenyl group, R 3 is independently an unsubstituted or substituted monovalent hydrocarbon group without a carbon-carbon double bond, R 4 is an oxygen atom or a divalent hydrocarbon group, and R 5 is It is independently a hydrogen atom, an alkyl group, an alkoxyalkyl group, or an acyl group, c is an integer of 1 to 250, and d is an integer of 1 to 3.), and has a viscosity of 10 to 10,000 mPa·s at 25°C. siloxane-based compounds having an alkenyl group and a hydrolyzable silyl group at the molecular chain terminal, and
(H) 분자 내에 탄소 원자수 6 이상의 알킬기를 갖는 알콕시실란 또는 그의 가수 분해 축합물(H) Alkoxysilane or hydrolytic condensate thereof having an alkyl group with 6 or more carbon atoms in the molecule
로부터 선택되는 1종류 또는 2종류 이상,One or two or more types selected from,
(I) 하이드로실릴화 반응 억제제, 접착 촉진제, 유기 용제 및 그 외 첨가제(I) Hydrosilylation reaction inhibitors, adhesion promoters, organic solvents and other additives
를 포함할 수도 있는 경화성 오가노폴리실록산 조성물, 그 경화물, 이것으로 이루어진 열전도성 부재, 이를 이용하는 방열 구조체 및 이들의 제조 방법에 의해 해결된다.The problem is solved by a curable organopolysiloxane composition that may include a cured product thereof, a heat conductive member made of the same, a heat dissipation structure using the same, and a manufacturing method thereof.
본 발명에 의해, 높은 열전도율을 가지면서, 가열 에이징 후에도 경화물의 경도 변화가 억제되고 있으며, 당해 경화물로 이루어진 열전도성 부재를 고온하에서 사용한 경우에도 유연성 및 응력 완화 특성을 유지할 수 있는 오가노폴리실록산 경화물을 부여하는 경화성 오가노폴리실록산 조성물이 제공된다. 또한, 본 발명에 의해, 당해 경화성 오가노폴리실록산 조성물을 경화시켜 이루어진 열전도성 부재, 상기 부재를 이용한 방열 구조체(특히, 전기·전자 부품의 방열 구조 및 이차전지의 방열 구조를 포함하는 전기·전자 기기의 방열 구조체)를 제공할 수 있다.According to the present invention, an organopolysiloxane resin that has high thermal conductivity, suppresses changes in hardness of the cured product even after heat aging, and maintains flexibility and stress relief properties even when a thermally conductive member made of the cured product is used at high temperature. Curable organopolysiloxane compositions that impart cargo are provided. In addition, according to the present invention, a heat conductive member formed by curing the curable organopolysiloxane composition, and a heat dissipation structure using the member (particularly, an electrical/electronic device including a heat dissipation structure for electrical/electronic components and a heat dissipation structure for a secondary battery) A heat dissipation structure) can be provided.
특히, 본 발명에 관한 경화성 오가노폴리실록산 조성물의 경화물은 고온하에서 사용한 경우에도 경도 변화가 억제되고 있기 때문에, 응력 완화성과 유연성이 우수하며, 다양한 형상을 구비한 방열 대상에 대해 적용한 경우, 고온하에서 장기간 사용해도 진동 등으로 발열성 부재로부터 박락(剝落)이나 공극(부재로부터의 부분적/일시적인 박리에 의한 공극 발생을 포함한다, 이하 동일)을 발생시키기 어렵고, 우수한 밀착성과 추종성을 계속 유지하기 때문에, 적응 초기의 방열 효율이 손상되지 않고 지속된다는 이점이 있다. 때문에, 종래품에 비해 방열 부재의 내구성 및 방열 퍼포먼스가 우수하고 또한 다양한 형상을 구비한 방열 대상에 적용할 수 있으며, 고온하에서의 조립·어셈블리에 사용해도 박락되기 어려운 동시에, 장기에 걸친 고온하에서의 방열 프로세스에 사용할 수 있는 이점을 갖는다.In particular, the cured product of the curable organopolysiloxane composition according to the present invention has suppressed changes in hardness even when used at high temperatures, and therefore has excellent stress relaxation and flexibility, and when applied to heat dissipation objects with various shapes, it can be used at high temperatures. Even when used for a long period of time, it is difficult to cause peeling or voids (including voids due to partial/temporary peeling from the member, hereinafter the same) from the heat-generating member due to vibration, etc., and excellent adhesion and followability are maintained. There is an advantage that the heat dissipation efficiency at the initial stage of adaptation continues without being damaged. Therefore, the durability and heat dissipation performance of the heat dissipation member is superior to that of conventional products, and it can be applied to heat dissipation objects with various shapes. It is also difficult to deteriorate even when used for assembling and assembling at high temperatures, and at the same time, it can be used in long-term heat dissipation processes under high temperatures. It has the advantage of being usable.
[경화성 오가노폴리실록산 조성물][Curable organopolysiloxane composition]
본 발명에 관한 조성물은 (A) 25℃에서의 점도가 10~100,000 mPa·s인 알케닐기 함유 오가노폴리실록산, (B) 오가노하이드로겐폴리실록산, (C) 열전도성 충전제, (D) 지방산, 지방산 에스테르 및 지방산 금속염으로부터 선택되는 적어도 1종류 이상(이하, 「지방산계 화합물」이라고 하는 경우가 있다), (E) 하이드로실릴화 반응용 촉매, (F) 내열성 부여제를 함유하여 이루어지며, 또한, 임의로 (G) (G1) 분자쇄 편말단에만 알콕시기를 갖는 특정 오가노폴리실록산, (G2) 분자쇄 말단에 알케닐기 및 가수 분해성 실릴기를 갖는 특정 실록산계 화합물, (H) 분자 내에 탄소 원자수 6 이상의 알킬기를 갖는 알콕시실란 또는 그의 가수 분해 축합물, 및 (I) 하이드로실릴화 반응 억제제, 접착 촉진제, 유기 용제 및 그 외 첨가제를 포함할 수도 있다. 또한, 본 발명에 관한 조성물은 1액형의 조성물일 수도, 2액형 등의 다성분형 조성물의 형태일 수도 있다. 이하, 각 성분 및 그의 첨가량 등에 대하여 설명한다.The composition according to the present invention includes (A) an alkenyl group-containing organopolysiloxane having a viscosity of 10 to 100,000 mPa·s at 25°C, (B) organohydrogenpolysiloxane, (C) a thermally conductive filler, (D) a fatty acid, It contains at least one type selected from fatty acid esters and fatty acid metal salts (hereinafter sometimes referred to as “fatty acid-based compounds”), (E) a catalyst for hydrosilylation reaction, (F) a heat resistance imparting agent, and , optionally (G) (G1) a specific organopolysiloxane having an alkoxy group only at one end of the molecular chain, (G2) a specific siloxane-based compound having an alkenyl group and a hydrolyzable silyl group at the end of the molecular chain, (H) 6 carbon atoms in the molecule. It may also contain an alkoxysilane or a hydrolyzed condensate thereof having the above alkyl group, and (I) a hydrosilylation reaction inhibitor, an adhesion promoter, an organic solvent, and other additives. Additionally, the composition according to the present invention may be a one-component composition or a multi-component composition such as a two-component composition. Hereinafter, each component and its addition amount will be explained.
[(A) 알케닐기 함유 오가노폴리실록산][(A) Organopolysiloxane containing alkenyl group]
성분 (A)인 알케닐기 함유 오가노폴리실록산은 본 조성물의 주제이며, 25℃에서의 점도가 10~100,000 mPa·s의 범위 내이다. (A) 성분의 25℃에서의 점도는 10~100, 00 mPa·s의 범위 내인 것이 바람직하고, 10~10,000 mPa·s의 범위 내인 것이 보다 바람직하다. (A) 성분의 점도가 10 mPa·s 미만이면, 얻어지는 오가노폴리실록산 경화물의 기계적 강도가 저하되는 경향이 있으며, 한편 100,000 mPa·s를 초과하면, 얻어지는 조성물이 너무 고점도이기 때문에, 취급 작업성 및 세부에의 도공성이 저하되는 경향이 있다.The alkenyl group-containing organopolysiloxane, which is component (A), is the main subject of the present composition, and has a viscosity in the range of 10 to 100,000 mPa·s at 25°C. The viscosity of the component (A) at 25°C is preferably in the range of 10 to 100,00 mPa·s, and more preferably in the range of 10 to 10,000 mPa·s. If the viscosity of component (A) is less than 10 mPa·s, the mechanical strength of the resulting cured organopolysiloxane tends to decrease, while if it exceeds 100,000 mPa·s, the resulting composition has too high a viscosity, making it difficult to handle and work. Coatability to details tends to decrease.
성분 (A)는 1종 또는 2종 이상의 알케닐기 함유 오가노폴리실록산으로 구성된다. 이러한 알케닐기 함유 오가노폴리실록산의 분자 구조는 특별히 한정되지 않으며, 예를 들어 직쇄상, 분지쇄상, 환상, 삼차원 망상 구조, 및 이들의 조합을 열거할 수 있다. 성분 (A)의 분자 내의 알케닐기로서, 비닐기, 알릴기, 부테닐기, 헥세닐기 등이 예시된다. 또한, 성분 (A) 중의 알케닐기 이외의 유기기로서, 메틸기 등의 알킬기; 페닐기 등의 아릴기; 3,3,3-트리플로로프로필기 등의 할로겐화 알킬기 등의 알케닐기를 제외한 1가 탄화수소기가 예시되며, 공업적으로는 메틸기 또는 페닐기가 바람직하다.Component (A) is composed of one or two or more types of alkenyl group-containing organopolysiloxane. The molecular structure of this alkenyl group-containing organopolysiloxane is not particularly limited, and examples include straight chain, branched chain, cyclic, three-dimensional network structures, and combinations thereof. Examples of the alkenyl group in the molecule of component (A) include vinyl group, allyl group, butenyl group, and hexenyl group. Additionally, organic groups other than alkenyl groups in component (A) include alkyl groups such as methyl groups; Aryl groups such as phenyl groups; Examples include monovalent hydrocarbon groups excluding alkenyl groups such as halogenated alkyl groups such as 3,3,3-trifluoropropyl groups, and industrially, methyl groups or phenyl groups are preferred.
특히 적합하게는, 성분 (A)는 직쇄상의 알케닐기 함유 오가노폴리실록산이며, 예를 들어 분자쇄 양말단 디메틸비닐실록시기 봉쇄 디메틸폴리실록산, 분자쇄 양말단 디메틸비닐실록시기 봉쇄 디메틸실록산·메틸페닐실록산 공중합체, 분자쇄 양말단 트리메틸실록시기 봉쇄 디메틸실록산·메틸비닐실록산 공중합체, 분자쇄 양말단 트리메틸실록시기 봉쇄 디메틸실록산·메틸비닐실록산·메틸페닐실록산 공중합체, 분자쇄 양말단 실라놀기 봉쇄 디메틸실록산·메틸비닐실록산 공중합체, 이들 중합체의 메틸기의 일부가 에틸기, 프로필기 등의 메틸기 이외의 알킬기나 3,3,3-트리플로로프로필기 등의 할로겐화 알킬기로 치환된 중합체, 이들 중합체의 비닐기가 알릴기, 부테닐기, 헥세닐기 등의 비닐기 이외의 알케닐기로 치환된 중합체, 및 이들 중합체의 2종 이상의 혼합물을 들 수 있다. 아울러, 이들 알케닐기 함유 오가노폴리실록산은 접점 장해 방지 등의 견지에서, 저분자량의 실록산 올리고머(옥타메틸테트라실록산(D4), 데카메틸펜타실록산(D5))가 저감 내지 제거되어 있는 것이 바람직하다.Particularly preferably, component (A) is an organopolysiloxane containing linear alkenyl groups, for example, dimethylpolysiloxane with dimethylvinylsiloxy groups blocked at both molecular chain ends, dimethylsiloxane and methylphenylsiloxane with dimethylvinylsiloxy groups blocked at both molecular chain ends. Copolymer, dimethylsiloxane·methylvinylsiloxane copolymer with blocked trimethylsiloxy groups at both ends of the molecular chain, dimethylsiloxane·methylvinylsiloxane·methylphenylsiloxane copolymer with blocked trimethylsiloxy groups at both ends of the molecular chain, dimethylsiloxane·methylvinylsiloxane with blocked silanol groups at both ends of the molecular chain Methylvinylsiloxane copolymers, polymers in which some of the methyl groups of these polymers are substituted with alkyl groups other than methyl groups such as ethyl or propyl groups, or halogenated alkyl groups such as 3,3,3-trifluoropropyl groups, and the vinyl groups of these polymers are allyl groups. Polymers substituted with alkenyl groups other than vinyl groups, such as polyethylene glycol groups, butenyl groups, and hexenyl groups, and mixtures of two or more types of these polymers. In addition, these alkenyl group-containing organopolysiloxanes preferably have low molecular weight siloxane oligomers (octamethyltetrasiloxane (D4), decamethylpentasiloxane (D5)) reduced or removed from the viewpoint of preventing contact failure.
[(B) 오가노하이드로겐폴리실록산][(B) Organohydrogenpolysiloxane]
성분 (B)는 본 발명의 조성물의 주된 가교제이며, 분자 내에 2개 이상의 규소 원자 결합 수소 원자를 갖는 오가노하이드로겐폴리실록산을 특별히 제한없이 이용할 수 있으나, 얻어지는 경화물의 유연성 및 기재에 대한 접착 유지성의 견지에서, 오가노하이드로겐폴리실록산의 분자 중의 규소 원자 결합 수소 원자의 개수(평균값)는 8개를 초과하지 않는 범위가 바람직하다. 특히, (B1) 25℃에서의 점도가 1~1,000 mPa·s이며, 분자 내에 평균적으로 2~4개의 규소 원자 결합 수소 원자를 함유하고, 그 중, 적어도 평균적으로 1개를 분자쇄 측쇄에 갖는 직쇄상의 오가노하이드로겐폴리실록산을 적어도 포함하는 것이 바람직하다.Component (B) is the main crosslinking agent in the composition of the present invention, and organohydrogenpolysiloxane having two or more silicon atom bonded hydrogen atoms in the molecule can be used without particular restrictions, but the flexibility of the resulting cured product and the adhesion retention to the substrate are limited. From this point of view, it is preferable that the number (average value) of hydrogen atoms bonded to silicon atoms in the organohydrogenpolysiloxane molecule does not exceed 8. In particular, (B1) has a viscosity at 25°C of 1 to 1,000 mPa·s, contains on average 2 to 4 silicon atom-bonded hydrogen atoms in the molecule, and has at least one on average in the side chain of the molecular chain. It is preferable that it contains at least linear organohydrogenpolysiloxane.
이러한 성분 (B1)은 분자쇄 양말단 트리메틸실록시기 봉쇄 메틸하이드로겐실록산·디메틸실록산 공중합체, 분자쇄 양말단 디메틸하이드로겐실록시기 봉쇄 메틸하이드로겐실록산·디메틸실록산 공중합체가 예시된다. 아울러, 이들 예시는 비한정적이며, 메틸기의 일부는 페닐기, 수산기, 알콕시기 등으로 치환되어 있을 수도 있다.Examples of such component (B1) include methylhydrogensiloxane·dimethylsiloxane copolymer with blocked trimethylsiloxy groups at both ends of the molecular chain and methylhydrogensiloxane·dimethylsiloxane copolymer with blocked dimethylhydrogensiloxy groups at both molecular chain ends. Additionally, these examples are non-limiting, and some of the methyl groups may be substituted with phenyl groups, hydroxyl groups, alkoxy groups, etc.
성분 (B1)의 25℃에서의 점도는 특별히 한정되지 않으나, 바람직하게는 1~500 mPa·s의 범위 내, 특히 바람직하게는 1~100 mPa·s의 범위 내이며, 또한 접점 장해 방지 등의 견지에서, 저분자량의 실록산 올리고머(옥타메틸테트라실록산(D4), 데카메틸펜타실록산(D5))가 저감 내지 제거되어 있는 것이 바람직하다.The viscosity of component (B1) at 25°C is not particularly limited, but is preferably within the range of 1 to 500 mPa·s, particularly preferably within the range of 1 to 100 mPa·s, and is also used to prevent contact failure, etc. From this point of view, it is preferable that low molecular weight siloxane oligomers (octamethyltetrasiloxane (D4), decamethylpentasiloxane (D5)) are reduced or eliminated.
[조성물 중의 오가노하이드로겐폴리실록산(가교제)의 양][Amount of organohydrogenpolysiloxane (crosslinking agent) in composition]
본 발명의 조성물은 성분 (B)에 대하여, 적어도 성분 (A)에 포함되는 알케닐기 1몰에 대하여, 성분 (B) 중의 규소 원자 결합 수소 원자가 0.1~10몰이 되는 양의 범위에 있는 것이 필요하며, 0.2~5.0몰이 되는 양, 0.3~3.0몰이 되는 양, 또는 0.4~2.0몰이 되는 양의 범위인 것이, 얻어지는 오가노폴리실록산 경화물의 기계적 강도와 접착 특성의 점에서 특히 바람직하다.The composition of the present invention requires that the amount of hydrogen atoms bonded to silicon atoms in component (B) be in the range of 0.1 to 10 moles, based on at least 1 mole of alkenyl groups contained in component (A). , an amount in the range of 0.2 to 5.0 mol, 0.3 to 3.0 mol, or 0.4 to 2.0 mol is particularly preferable in terms of mechanical strength and adhesive properties of the obtained cured organopolysiloxane.
[(C) 열전도성 충전제][(C) Thermal conductive filler]
성분 (C)는 본 조성물 및 본 조성물을 경화시켜 이루어진 열전도성 부재에 열전도성을 부여하기 위한 열전도성 충전제이다. 이러한 성분 (C)로서는, 순금속, 합금, 금속 산화물, 금속 수산화물, 금속 질화물, 금속 탄화물, 금속 규화물, 탄소, 연자성 합금 및 페라이트로 이루어진 군으로부터 선택된 적어도 1종 이상의 분말 및/또는 파이버인 것이 바람직하며, 금속계 분말, 금속 산화물계 분말, 금속 질화물계 분말, 또는 탄소 분말이 적합하다. 성분 (C)의 형상은 특별히 한정되지 않으나, 예를 들어 구상, 침상, 원반상, 봉상, 부정형상을 들 수 있으며, 바람직하게는 구상, 부정형상이다. 또한, 성분 (C)의 평균 입자 지름은 특별히 한정되지 않으나, 바람직하게는 0.01~500 μm의 범위 내이며, 더욱 바람직하게는 0.01~300 μm의 범위 내이다.Component (C) is a thermally conductive filler for imparting thermal conductivity to the present composition and to the thermally conductive member formed by curing the present composition. This component (C) is preferably at least one type of powder and/or fiber selected from the group consisting of pure metal, alloy, metal oxide, metal hydroxide, metal nitride, metal carbide, metal silicide, carbon, soft magnetic alloy, and ferrite. Metal-based powder, metal oxide-based powder, metal nitride-based powder, or carbon powder are suitable. The shape of component (C) is not particularly limited, but examples include spherical shape, needle shape, disk shape, rod shape, and irregular shape, and preferably spherical shape and irregular shape. Additionally, the average particle diameter of component (C) is not particularly limited, but is preferably within the range of 0.01 to 500 μm, and more preferably within the range of 0.01 to 300 μm.
성분 (C)로서 적합하게는, 은 분말, 알루미늄 분말, 산화알루미늄 분말, 산화아연 분말, 산화마그네슘 분말, 질화알루미늄 분말 또는 그래파이트이다. 또한, 본 조성물에 전기 절연성이 요구되는 경우에는, 금속 산화물계 분말 또는 금속 질화물계 분말인 것이 바람직하고, 특히 산화알루미늄 분말, 산화아연 분말, 산화마그네슘 분말 또는 질화알루미늄 분말인 것이 바람직하다.Suitable components (C) include silver powder, aluminum powder, aluminum oxide powder, zinc oxide powder, magnesium oxide powder, aluminum nitride powder, or graphite. In addition, when electrical insulation is required for the composition, it is preferable to use a metal oxide-based powder or a metal nitride-based powder, and especially aluminum oxide powder, zinc oxide powder, magnesium oxide powder, or aluminum nitride powder.
이와 같은 열전도성 충전제는 후술하는 성분 (G)인 적어도 편말단에 알콕시기를 갖는 실록산계 화합물 및/또는 성분 (H)인 장쇄 알킬기를 갖는 알콕시실란에 의해, 그의 전부 또는 일부에 대해 표면 처리가 이루어져 있을 수 있고 또한 바람직하다. 또한, 이들 성분과 함께, 이들 분체 및/또는 파이버로서, 커플링제로서 알려져 있는 각종 표면 처리제에 의해 처리되어 있는 것을 사용할 수도 있다. 성분 (C)의 분체 및/또는 파이버를 처리하기 위한 표면 처리제로서는, 성분 (G), 성분 (H) 외, 계면활성제, 그 외 실란 커플링제, 알루미늄계 커플링제 및 실리콘계 표면 처리제 등을 열거할 수 있다.Such a thermally conductive filler is surface treated in whole or in part with a siloxane-based compound having an alkoxy group at least at one end as component (G), which will be described later, and/or an alkoxysilane having a long-chain alkyl group as component (H). It is possible and desirable. In addition to these components, powders and/or fibers that have been treated with various surface treatment agents known as coupling agents can also be used. Surface treatment agents for treating the powder and/or fiber of component (C) include component (G), component (H), surfactants, other silane coupling agents, aluminum-based coupling agents, and silicon-based surface treatment agents. You can.
성분 (C)는 그 충전 효율을 개선하기 위해, 예를 들어 입경이 큰 분말과 입경이 작은 분말을 최밀 충전 이론 분포 곡선에 따른 비율로 조합함으로써, 충전 효율이 향상되고, 저점도화 및 고열전도화가 가능해진다. 본 발명에서는, (C1) 평균 입경이 0.01~100 μm인 구상 및 파쇄상의 산화알루미늄 분말, (C2) 평균 입경이 0.01~100 μm인 구상 및 파쇄상의 산화마그네슘 분말, (C3) 평균 입경이 0.01~50 μm인 부정형의 질화알루미늄 분말로부터 선택되며, 충전 효율을 개선하기 위해 입자 지름 또는 형상이 상이한 2종류 이상의 혼합물을 사용할 수도 있고 또한 바람직하다.In order to improve the filling efficiency of component (C), for example, by combining powder with a large particle size and powder with a small particle size in a ratio according to the closest packing theory distribution curve, the filling efficiency is improved, and the viscosity is reduced and the heat conductivity is improved. It becomes possible. In the present invention, (C1) spherical and crushed aluminum oxide powder with an average particle diameter of 0.01 to 100 μm, (C2) spherical and crushed magnesium oxide powder with an average particle diameter of 0.01 to 100 μm, (C3) 0.01 to 100 μm average particle size. It is selected from 50 μm amorphous aluminum nitride powder, and a mixture of two or more types with different particle diameters or shapes may be used to improve charging efficiency, and is also preferred.
[성분 (C)의 함유량][Content of component (C)]
본 발명에 있어서, 높은 열전도율을 달성하기 위해, 성분 (C)의 함유량은 조성물 중의 고형분(경화 반응에 의해 경화물을 형성하는 성분) 전체에 대하여 60~90 부피%의 범위이며, 65~90 부피%의 범위, 70~90 부피%의 범위, 70~85 부피%의 범위인 것이 바람직하다. 성분 (C)의 함유량이 상기 하한 미만이면, 얻어지는 조성물의 열전도성이 2.0 W/mK 미만이 되어, 목적으로 하는 높은 열전도율을 실현할 수 없게 되는 경우가 있다. 한편, 상기 범위의 상한을 초과하면, 후술하는 성분 (C)의 사용이나, 성분 (G), 성분 (H)를 배합 또는 성분 (C)의 표면 처리에 이용한 경우에도, 얻어지는 조성물의 점도가 현저히 높아지거나, 초기 경화물이 현저히 단단해져, 그의 취급 작업성 및 기재에 대한 응력 완화 특성이나 밀착성 등이 저하되는 경우가 있다.In the present invention, in order to achieve high thermal conductivity, the content of component (C) is in the range of 60 to 90% by volume, 65 to 90% by volume, based on the total solid content (component that forms the cured product by curing reaction) in the composition. It is preferable that it is in the range of %, 70 to 90 volume %, and 70 to 85 volume %. If the content of component (C) is less than the above lower limit, the thermal conductivity of the resulting composition may be less than 2.0 W/mK, making it impossible to achieve the desired high thermal conductivity in some cases. On the other hand, if the upper limit of the above range is exceeded, even when the component (C) described later is used, or when the component (G) or component (H) is mixed or used for surface treatment of component (C), the viscosity of the resulting composition is significantly lowered. This may increase, or the initial cured product may become significantly hard, and its handling workability, stress relief characteristics and adhesion to the base material may deteriorate.
아울러, 성분 (C)의 사용량은 성분 (A) 100 질량부에 대하여 600~4500 질량부의 범위인 것이 더욱 바람직하며, 800~4000 질량부의 범위인 것이 특히 바람직하다. 성분 (C)의 사용량이 상기 부피%의 범위인 동시에, 성분 (A)에 대한 사용량이 상기 범위를 만족하는 경우, 본 발명의 과제를 특히 적합하게 해결 가능하다.In addition, the amount of component (C) used is more preferably in the range of 600 to 4,500 parts by mass, and particularly preferably in the range of 800 to 4,000 parts by mass, based on 100 parts by mass of component (A). If the amount of component (C) used is within the above volume percentage range and the amount of component (A) used satisfies the above range, the problem of the present invention can be particularly suitably solved.
[그 외 무기 충전제][Other inorganic fillers]
본 발명의 조성물은 임의 성분으로서, 예를 들어 흄드 실리카, 습식 실리카, 분쇄 석영, 산화티탄, 탄산 마그네슘, 산화아연, 산화철, 규조토, 카본 블랙 등의 무기 충전제(「무기 충전재」라고도 한다), 이러한 무기 충전제의 표면을 후술하는 성분 (G), 성분 (H) 및/또는 그 외 유기 규소 화합물(실라잔류 등)에 의해 소수 처리하여 이루어진 무기 충전제를 배합할 수도 있다. 본 발명의 기술적 효과, 특히 높은 열전도성 및 경화물의 유연성과 응력 완화 특성, 기재에 대한 밀착성을 양립하는 견지에서는, 성분 (C) 이외의 충전제를 실질적으로 포함하지 않는 조성일 수 있다. 한편, 기계적 강도의 개선(보강)이나 점도 조정 등의 그 외 기능을 목적으로 상기 충전제를 본 발명의 기술적 효과를 해치지 않는 범위에서 병용할 수도 있고 또한 본 발명의 바람직한 실시형태의 하나로 포함된다.The composition of the present invention includes, as optional components, inorganic fillers such as fumed silica, wet silica, crushed quartz, titanium oxide, magnesium carbonate, zinc oxide, iron oxide, diatomaceous earth, and carbon black (also referred to as “inorganic fillers”), such as An inorganic filler prepared by hydrophobically treating the surface of the inorganic filler with component (G), component (H), and/or other organic silicon compounds (silazanes, etc.) described later can also be blended. From the viewpoint of achieving the technical effects of the present invention, especially high thermal conductivity, flexibility and stress relaxation characteristics of the cured product, and adhesion to the substrate, the composition may be substantially free of fillers other than component (C). On the other hand, for the purpose of other functions such as improvement (reinforcement) of mechanical strength or viscosity adjustment, the above filler may be used together within a range that does not impair the technical effect of the present invention, and is included as one of the preferred embodiments of the present invention.
[성분 (C)의 표면 처리][Surface treatment of component (C)]
본 발명에 관한 성분 (C)는 후술하는 성분 (G) 및/또는 성분 (H)에 의해 표면 처리되어 있는 것이 바람직하다. 이들 성분에 의한 표면 처리 방법은 특별히 제한되는 것은 아니지만, 성분 (C)인 열전도성 무기 충전제에의 직접 처리법, 인터그랄 블렌드(Integral blend)법, 드라이 콘센트레이트법 등을 사용할 수 있다. 본 발명에 있어서, 조성물 전체로서의 충전성 및 경화물의 접착 강도 개선의 견지에서, 상기 성분 (A)의 일부 또는 전부와 성분 (G) 및 성분 (H)를 미리 혼합해 두고, 당해 혼합물 중에 성분 (C)를 순차 혼합하고 균일화한 후에 가열(베이스 히트)하는 가열 표면 처리법을 가장 적합하게 예시할 수 있다. 당해 표면 처리법은 감압하에서, 100~200℃에서 당해 혼합물을 가열 교반할 수 있으며, 온도 조건 및 교반 시간은 샘플의 양에 따라 설계 가능하지만, 120~180℃ 및 0.25~10시간의 범위가 바람직하다. 아울러, 성분 (C)의 표면 처리 공정은 임의이지만, 본 조성물의 유동성, 갭필성(gap-fill) 및 요변성 개선의 견지에서, 성분 (G)에 의해 성분 (C)가 적어도 일부가 표면 처리되고, 이어서 성분 (H)에 의해 성분 (C)가 표면 처리되어 있는 공정을 포함하는, 단계적인 처리 공정일 수도 있다.Component (C) according to the present invention is preferably surface treated with component (G) and/or component (H) described later. The surface treatment method using these components is not particularly limited, but direct treatment of the thermally conductive inorganic filler that is component (C), integral blend method, dry concentrate method, etc. can be used. In the present invention, from the viewpoint of improving the fillability of the composition as a whole and the adhesive strength of the cured product, part or all of the component (A), component (G), and component (H) are mixed in advance, and in the mixture, the component ( The most suitable example is a heating surface treatment method in which C) is sequentially mixed and homogenized and then heated (base heat). This surface treatment method can heat and stir the mixture at 100-200°C under reduced pressure, and the temperature conditions and stirring time can be designed depending on the amount of sample, but the range of 120-180°C and 0.25-10 hours is preferable. . In addition, the surface treatment process of component (C) is optional, but from the viewpoint of improving the fluidity, gap-fill, and thixotropy of the present composition, at least a portion of component (C) is surface treated by component (G). It may be a stepwise treatment process including a step in which component (C) is then surface treated with component (H).
상기 혼합에 사용하는 장치로서는 특별히 한정이 없으며, 일축 또는 이축의 연속 혼합기, 쌍롤(twin roll), 로스 믹서, 호바트 믹서, 덴탈 믹서, 플래니터리 믹서, 니더 믹서, 헨셀 믹서 등이 예시된다.There is no particular limitation on the apparatus used for the mixing, and examples include a single- or dual-axis continuous mixer, twin roll, Ross mixer, Hobart mixer, dental mixer, planetary mixer, kneader mixer, and Henschel mixer.
[(D) 지방산계 화합물][(D) Fatty acid-based compounds]
성분 (D)는 본 조성물 및 본 조성물을 경화시켜 이루어진 실리콘계의 열전도성 부재인 경화물에 대하여, 가열 에이징 시의 경도 변화를 억제하는 성분이다. 특히, 성분 (C)인 열전도성 충전제의 배합량이 상기 범위에 있는 경우, 성분 (D)를 사용하지 않는 경우에는, 경화물의 가열 에이징 시에 급격하게 단단해져, 그의 응력 완화성, 유연성 및 기재 밀착성 등이 손상되는 경우가 있지만, 성분 (D)와, 적합하게는 후술하는 성분 (F)를 하이드로실릴화 경화 반응성 조성물에서 병용함으로써, 얻어지는 경화물은 높은 열전도율을 가지며, 또한 초기 경도를 유지하며, 양호한 응력 완화성, 유연성 및 기재 밀착성을 실현할 수 있다.Component (D) is a component that suppresses changes in hardness during heat aging with respect to the present composition and the cured product, which is a silicone-based thermal conductive member, obtained by curing the present composition. In particular, when the compounding amount of the thermally conductive filler as component (C) is within the above range and when component (D) is not used, the cured product suddenly hardens during heat aging, and its stress relaxation properties, flexibility, and base material adhesion, etc. Although this may be damaged, by using component (D) and component (F), suitably described later, in combination in a hydrosilylation curing reactive composition, the resulting cured product has high thermal conductivity, maintains initial hardness, and has good Stress relaxation, flexibility, and substrate adhesion can be achieved.
성분 (D)는 구체적으로는, 지방산, 지방산 에스테르 및 지방산 금속염으로부터 선택되는 적어도 1종류 이상이며, 카프로산, 카프릴산, 펠라르곤산, 카프르산, 운데칸산, 라우르산, 미리스트산, 팔미트산, 스테아르산, 베헨산, 올레산 등의 지방산; 그 알킬 에스테르인 지방산 에스테르; 나트륨, 리튬, 칼륨 등의 지방산의 알칼리 금속염; 칼슘 등의 지방산의 알칼리 토류 금속염을 예시할 수 있다. 적합하게는, 성분 (D)는 (D1) 포화 지방산 및 포화 지방산 금속염으로부터 선택되는 적어도 1종류 이상이며, (D1-1) 스테아르산, 스테아르산의 알칼리 금속염, 스테아르산의 알칼리 토류 금속염으로부터 선택되는 1종 이상인 것이 특히 바람직하다.Component (D) is specifically, at least one selected from fatty acids, fatty acid esters, and fatty acid metal salts, and includes caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, and myristic acid. , fatty acids such as palmitic acid, stearic acid, behenic acid, and oleic acid; fatty acid esters thereof, which are alkyl esters; Alkali metal salts of fatty acids such as sodium, lithium, and potassium; Examples include alkaline earth metal salts of fatty acids such as calcium. Suitably, component (D) is (D1) at least one selected from saturated fatty acids and saturated fatty acid metal salts, and (D1-1) selected from stearic acid, alkali metal salts of stearic acid, and alkaline earth metal salts of stearic acid. It is particularly preferable that there is more than one type.
성분 (D)가 특히 성분 (F)와의 병용계로 경화물의 경도 변화를 억제하는 작용 기작은 명확히 특정되지 않았지만, 지방산, 지방산염(비누), 지방산 에스테르 등의 지방산계 화합물이 성분 (F)의 존재하에서 내열성이 개선된 실리콘 경화물 매트릭스 내에 한정된 양 존재함으로써, 열전도성 충전제의 입자 표면 내지 근방에 이들 지방산계 화합물로 이루어진 내수성 및 윤활성의 박막 또는 국소 구조가 형성되어, 고온하에서의 입자 표면을 화학적으로 저활성 내지 불활성화하는 동시에, 열전도성 충전제의 표면끼리의 응집이나 조대 입자의 형성을 효과적으로 방지하고 있는 것이 아닌지 추측된다. 다만, 후술하는 바와 같이, 성분 (D)는 열전도성 충전제의 표면 처리제로서 사용하지 않아도, 단순히 다른 성분과 균일 혼합하는 것만으로 기술적 효과를 발휘하기 때문에, 본 발명에서 조성물 중에 성분 (D)를 첨가하는 타이밍이 한정되는 것은 아니다.The mechanism of action of component (D), especially in combination with component (F), to suppress changes in hardness of the cured product has not been clearly identified, but the presence of fatty acid-based compounds such as fatty acids, fatty acid salts (soap), and fatty acid esters in component (F) By existing in a limited amount in the silicone cured material matrix with improved heat resistance under low temperature, a water-resistant and lubricating thin film or local structure composed of these fatty acid-based compounds is formed on or near the particle surface of the thermally conductive filler, thereby chemically reducing the particle surface at high temperatures. It is assumed that while activating or deactivating the heat conductive filler, it effectively prevents agglomeration between the surfaces of the thermally conductive filler and the formation of coarse particles. However, as will be described later, component (D) exerts a technical effect simply by uniformly mixing with other components even if it is not used as a surface treatment agent for the heat conductive filler, so component (D) is added to the composition in the present invention. The timing is not limited.
성분 (D)의 배합량은 열전도성 충전제인 성분 (C)(복수로 이루어진 경우에는 총량) 100 질량부에 대하여 0.05~2.0 질량부의 범위일 필요가 있다. 본 발명의 기술적 효과를 달성하기 위해서는, 성분 (D)의 배합량은 상기 범위일 필요가 있으며, 상기 범위는 임계적 의의를 갖는다. 즉, 성분 (D)의 배합량이 상기 하한 미만이면, 설령 성분 (F)와 병용하더라도 경화물의 경도 변화를 억제할 수 없는 경우가 있다(예를 들어, 후술하는 비교예 1, 비교예 3). 한편, 성분 (D)의 배합량이 상기 상한을 초과하면, 경화물의 경도 변화를 억제할 수 없는 경우가 있다(예를 들어, 후술하는 비교예 4).The mixing amount of component (D) needs to be in the range of 0.05 to 2.0 parts by mass based on 100 parts by mass of component (C), which is a thermally conductive filler (total amount in case of multiple components). In order to achieve the technical effect of the present invention, the compounding amount of component (D) needs to be within the above range, and the above range has critical significance. That is, if the compounding amount of component (D) is less than the above lower limit, the change in hardness of the cured product may not be suppressed even if used in combination with component (F) (for example, Comparative Examples 1 and 3 described later). On the other hand, if the compounding amount of component (D) exceeds the above upper limit, the change in hardness of the cured product may not be suppressed (for example, Comparative Example 4 described later).
[(E) 하이드로실릴화 반응용 촉매][(E) Catalyst for hydrosilylation reaction]
하이드로실릴화 반응용 촉매는 본 조성물의 경화에 필요한 성분이며, 백금계 촉매, 로듐계 촉매, 팔라듐계 촉매가 예시되고, 본 조성물의 경화를 현저하게 촉진할 수 있기 때문에 백금계 촉매가 바람직하다. 이 백금계 촉매로서는, 백금 미분말, 염화백금산, 염화백금산의 알코올 용액, 백금-알케닐실록산 착체, 백금-올레핀 착체, 백금-카보닐 착체, 및 이들 백금계 촉매를 실리콘 수지, 폴리카보네이트 수지, 아크릴 수지 등의 열가소성 수지로 분산 혹은 캡슐화한 촉매가 예시되며, 특히 백금-알케닐실록산 착체가 바람직하다. 특히, 백금의 1,3-디비닐-1,1,3,3-테트라메틸디실록산 착체인 것이 바람직하며, 당해 착체의 알케닐실록산 용액의 형태로 첨가하는 것이 바람직하다. 덧붙여, 취급 작업성 및 조성물의 가사 시간(pot life) 개선의 견지에서, 열가소성 수지로 분산 혹은 캡슐화한 미립자상의 백금 함유 하이드로실릴화 반응 촉매를 이용할 수도 있다. 아울러, 하이드로실릴화 반응을 촉진하는 촉매로서는, 철, 루테늄, 철/코발트 등의 비백금계 금속 촉매를 이용할 수도 있다.The catalyst for the hydrosilylation reaction is a necessary component for curing the present composition. Examples include a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst. A platinum-based catalyst is preferred because it can significantly accelerate the curing of the present composition. As this platinum-based catalyst, platinum fine powder, chloroplatinic acid, alcohol solution of chloroplatinic acid, platinum-alkenylsiloxane complex, platinum-olefin complex, platinum-carbonyl complex, and these platinum-based catalysts can be mixed with silicone resin, polycarbonate resin, or acrylic. Catalysts dispersed or encapsulated in thermoplastic resins such as resins are examples, and platinum-alkenylsiloxane complexes are particularly preferable. In particular, it is preferable that it is a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum, and it is preferable to add the complex in the form of an alkenylsiloxane solution. Additionally, from the viewpoint of improving handling and pot life of the composition, a hydrosilylation reaction catalyst containing platinum in fine particles dispersed or encapsulated in a thermoplastic resin may be used. In addition, as a catalyst to promote the hydrosilylation reaction, non-platinum-based metal catalysts such as iron, ruthenium, and iron/cobalt can also be used.
한편, 하이드로실릴화 반응용 촉매로서는, (메틸사이클로펜타디에닐)트리메틸 백금(IV) 착체, 비스(2,4-펜탄디오나토) 백금(II) 착체 등의 이른바 고에너지선 활성화 촉매 또는 광활성화 촉매를 사용할 수도 있다. 이러한 하이드로실릴화 반응용 촉매를 사용함으로써, 조성물 전체로서 고에너지선의 조사를 트리거로 하여 저온에서도 경화가 가능하고, 보존 안정성이 우수하며, 또한 반응의 컨트롤이 용이하기 때문에, 취급 작업성이 우수하다는 특성을 실현할 수 있는 경우가 있다. 이 경우, 고에너지선으로서, 자외선이 촉매 활성화 효율의 점에서 바람직하며, 파장 280~380 nm의 범위의 자외선이 공업적 이용의 견지에서 바람직하다. 또한, 조사량은 고에너지선 활성형 촉매의 종류에 따라 상이하지만, 자외선의 경우에는 파장 365 nm에서의 적산 조사량이 100 mJ/cm2~100 J/cm2의 범위 내인 것이 바람직하다.On the other hand, as catalysts for hydrosilylation reaction, so-called high-energy ray activated catalysts or photoactivated catalysts such as (methylcyclopentadienyl)trimethyl platinum(IV) complex and bis(2,4-pentanedionato)platinum(II) complex. A catalyst can also be used. By using such a catalyst for hydrosilylation reaction, the composition as a whole can be cured even at low temperatures by triggering irradiation of high-energy rays, has excellent storage stability, and the reaction is easy to control, so handling workability is excellent. There are cases where characteristics can be realized. In this case, as a high-energy ray, ultraviolet rays are preferable in terms of catalyst activation efficiency, and ultraviolet rays with a wavelength in the range of 280 to 380 nm are preferable from the viewpoint of industrial use. Additionally, the irradiation amount varies depending on the type of high-energy ray-activated catalyst, but in the case of ultraviolet rays, it is preferable that the integrated irradiation amount at a wavelength of 365 nm is within the range of 100 mJ/cm 2 to 100 J/cm 2 .
하이드로실릴화 반응용 촉매의 첨가량은 촉매량이면 무방하며, 보다 구체적으로는 조성물 전체에 대하여, 금속 원자가 질량 단위로 0.01~500 ppm의 범위 내가 되는 양, 0.01~100 ppm의 범위 내가 되는 양, 혹은 0.01~50 ppm의 범위 내가 되는 양인 것이 바람직하다.The amount of catalyst for hydrosilylation reaction may be any catalytic amount, and more specifically, the amount of metal atoms in the entire composition is within the range of 0.01 to 500 ppm, 0.01 to 100 ppm, or 0.01 ppm. It is preferable that the amount is within the range of ~50 ppm.
[(F) 내열성 부여제][(F) Heat resistance imparting agent]
본 발명에 관한 조성물 및 그의 경화물은 전술한 (D) 지방산계 화합물을 일정량 포함하는 동시에, (F) 내열성 부여제를 병용함으로써 그 기술적 효과를 실현할 수 있다. 내열성 부여제의 배합량은 조성물 전체(고형분)의 0.01~5.0질량%의 범위일 수 있으며, 0.05~2.0질량%, 0.07~0.5질량%의 범위일 수도 있다.The composition and its cured product according to the present invention can realize its technical effect by containing a certain amount of the above-mentioned (D) fatty acid-based compound and simultaneously using (F) a heat resistance imparting agent. The amount of the heat resistance imparting agent may be in the range of 0.01 to 5.0 mass%, 0.05 to 2.0 mass%, or 0.07 to 0.5 mass% of the total composition (solid content).
내열성 부여제는, 예를 들어 산화철, 산화티탄, 산화세륨, 산화마그네슘, 산화아연 등의 금속 산화물, 수산화세륨 등의 금속 수산화물, 프탈로시아닌 화합물, 세륨 실라놀레이트, 세륨 지방산염, 오가노폴리실록산과 세륨의 카복실산염의 반응 생성물 등을 열거할 수 있다. 특히 적합하게는, (F1) 프탈로시아닌 화합물이며, 예를 들어 일본 공표특허공보 제2014-503680호에 개시된 무금속 프탈로시아닌 화합물 및 금속 함유 프탈로시아닌 화합물로 이루어진 군으로부터 선택되는 첨가제가 적합하게 사용되며, 금속 함유 프탈로시아닌 화합물 중, 구리 프탈로시아닌 화합물이 특히 적합하다. 가장 적합 하고 비한정적인 내열성 부여제의 일 예는 29H, 31H-프탈로시아니나토(2-)-N29,N30,N31,N32 구리이다. 이러한 프탈로시아닌 화합물은 시판되고 있으며, 예를 들어 PolyOne Corporation(Avon Lake, Ohio, USA)의 Stan-tone(상표) 40SP03이 있다.Heat resistance imparting agents include, for example, metal oxides such as iron oxide, titanium oxide, cerium oxide, magnesium oxide, and zinc oxide, metal hydroxides such as cerium hydroxide, phthalocyanine compounds, cerium silanolate, cerium fatty acid salt, organopolysiloxane, and cerium. Reaction products of carboxylic acid salts, etc. can be listed. Particularly suitably used are (F1) phthalocyanine compounds, and for example, additives selected from the group consisting of metal-free phthalocyanine compounds and metal-containing phthalocyanine compounds disclosed in Japanese Patent Publication No. 2014-503680 are suitably used, and metal-containing compounds. Among the phthalocyanine compounds, copper phthalocyanine compounds are particularly suitable. best fit A non-limiting example of a heat resistance imparting agent is 29H, 31H-phthalocyaninato(2-)-N29, N30, N31, N32 copper. Such phthalocyanine compounds are commercially available, for example, Stan-tone (trademark) 40SP03 from PolyOne Corporation (Avon Lake, Ohio, USA).
[(G) 분자쇄 편말단에 알콕시기를 갖는 실록산계 화합물][(G) Siloxane-based compound having an alkoxy group at one end of the molecular chain]
성분 (G)는 본 발명에 관한 조성물의 임의의 구성이며, (G1) 분자쇄 편말단에만 알콕시기를 갖는 특정 오가노폴리실록산 및 (G2) 분자쇄 말단에 알케닐기 및 가수 분해성 실릴기를 갖는 특정 실록산계 화합물로부터 선택되는 1종류 이상이다. 이들은 분자쇄 편말단에 알콕시기를 가지며, 또한 적어도 일부에 폴리실록산 구조를 갖는 표면 처리제이며, 성분 (C)인 열전도성 충전제의 적어도 일부에 대해 성분 (G)에 의한 표면 처리를 수행함으로써, 성분 (D)인 열전도성 충전제가 대량으로 배합되어도, 본 조성물의 유동성, 갭필성 및 요변성이 개선된 경화성 오가노폴리실록산 조성물을 제공할 수 있다.Component (G) is an arbitrary component of the composition according to the present invention, including (G1) a specific organopolysiloxane having an alkoxy group only at one end of the molecular chain and (G2) a specific siloxane type having an alkenyl group and a hydrolyzable silyl group at the end of the molecular chain. It is one or more types selected from compounds. These are surface treatment agents that have an alkoxy group at one end of the molecular chain and have a polysiloxane structure at least in part. By performing surface treatment with component (G) on at least a part of the thermally conductive filler that is component (C), component (D) ), even if a large amount of thermally conductive fillers are mixed, it is possible to provide a curable organopolysiloxane composition with improved fluidity, gap filling properties, and thixotropy of the composition.
성분 (G)는 성분 (G1) 및 성분 (G2)로부터 선택되는 1종류 이상이며, 어느 하나만을 사용할 수도 있고, 양자를 혼합물 등의 형태로 병용할 수도 있다. 본 발명에 있어서, 특히 아주 알맞은 성분 (G)는 분자쇄 편말단에 트리알콕시실릴기 또는 트리알콕시실록시기를 갖는 것이다.Component (G) is one or more types selected from component (G1) and component (G2), and either one may be used alone, or both may be used together in the form of a mixture or the like. In the present invention, a particularly suitable component (G) is one having a trialkoxysilyl group or trialkoxysiloxy group at one end of the molecular chain.
성분 (G1)은 일반식 (1):Component (G1) has the general formula (1):
[화 2][Tuesday 2]
로 표시되고, 25℃에서의 점도가 10~10,000 mPa·s 미만인 오가노폴리실록산이다.It is an organopolysiloxane with a viscosity of 10 to less than 10,000 mPa·s at 25°C.
일반식 (1) 중, R1은 독립적으로 비치환 또는 치환된 탄소-탄소 이중 결합을 갖지 않는 1가의 탄화수소기이며, 그의 예로서는, 직쇄상 알킬기, 분지쇄상 알킬기, 환상 알킬기, 아릴기, 아르알킬기, 할로겐화 알킬기를 들 수 있다. 공업적으로는, R1은 바람직하게는 메틸기 또는 페닐기이며, 내열성의 견지에서 메틸기가 바람직하다.In General Formula (1), R 1 is independently an unsubstituted or substituted monovalent hydrocarbon group without a carbon-carbon double bond, examples thereof include a straight-chain alkyl group, a branched-chain alkyl group, a cyclic alkyl group, an aryl group, and an aralkyl group. , and halogenated alkyl groups. Industrially, R 1 is preferably a methyl group or a phenyl group, and a methyl group is preferable from the viewpoint of heat resistance.
R2는 독립적으로 수소 원자, 알킬기, 알콕시알킬기, 알케닐기 또는 아실기이다. 표면 처리의 견지에서 R2는 알킬기인 것이 바람직하고, 특히는 메틸기, 에틸기인 것이 바람직하다.R 2 is independently a hydrogen atom, an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group. From the viewpoint of surface treatment, R 2 is preferably an alkyl group, and particularly preferably a methyl group or an ethyl group.
일반식 (1) 중, a는 5~250의 범위의 정수이며, 10~200의 범위가 바람직하다. 또한, b는 1~3의 정수이며, 바람직하게는 2 또는 3이다. 본 발명에 관한 성분 (G1)로서 적합하게는, b는 3이고, 분자쇄 편말단에 트리알콕시실록시기를 가지며, R1이 메틸기인 폴리디메틸실록산이 적합하게 예시된다.In General Formula (1), a is an integer in the range of 5 to 250, and preferably in the range of 10 to 200. Additionally, b is an integer of 1 to 3, and is preferably 2 or 3. A suitable example of the component (G1) according to the present invention is polydimethylsiloxane, where b is 3, has a trialkoxysiloxy group at one end of the molecular chain, and R 1 is a methyl group.
성분 (G2)는Component (G2) is
일반식 (2):General formula (2):
RalkR3 2SiO(R3 2SiO)cR3 2Si-R4-SiR3 (3-d)(OR5)d R alk R 3 2 SiO(R 3 2 SiO) c R 3 2 Si-R 4 -SiR 3 (3-d) (OR 5 ) d
로 표시되고, 25℃에서의 점도가 10~10,000 mPa·s의 범위에 있는, 분자쇄 말단에 알케닐기 및 가수 분해성 실릴기를 갖는 실록산계 화합물이다.It is a siloxane-based compound having an alkenyl group and a hydrolyzable silyl group at the end of the molecular chain, which is expressed as , and has a viscosity in the range of 10 to 10,000 mPa·s at 25°C.
여기서, Ralk는 알케닐기이며, 비닐기, 알릴기, 헥세닐기 등의 탄소 원자수 2~10의 알케닐기가 예시된다. 성분 (G2)는 분자쇄의 편말단에 알케닐기를 갖기 때문에, 성분 (C)와 병용한 경우의 경화성 및 접착 특성을 개선할 수 있는 경우가 있다.Here, R alk is an alkenyl group, and examples include alkenyl groups having 2 to 10 carbon atoms, such as vinyl group, allyl group, and hexenyl group. Since component (G2) has an alkenyl group at one end of the molecular chain, curability and adhesive properties may be improved when used in combination with component (C).
식 중, R3은 독립적으로 비치환 또는 치환된 탄소-탄소 이중 결합을 갖지 않는 1가 탄화수소기이며, 직쇄상 알킬기, 분지쇄상 알킬기, 환상 알킬기, 알케닐기, 아릴기, 아르알킬기, 할로겐화 알킬기를 들 수 있고, 공업적 견지에서는 메틸기 또는 페닐기이며, 내열성의 견지에서 메틸기가 바람직하다. R4는 산소 원자 또는 2가 탄화수소기이다. R4인 2가 탄화수소기로서는, 메틸렌기 등의 알킬렌기; 에틸렌 옥시 에틸렌기, 에틸렌 옥시 프로필렌기 등의 알킬렌 옥시알킬렌기를 들 수 있다. 한편, R4는 산소 원자일 수 있고 또한 바람직하다.In the formula, R 3 is independently an unsubstituted or substituted monovalent hydrocarbon group without a carbon-carbon double bond, and may be a straight-chain alkyl group, a branched-chain alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a halogenated alkyl group. Examples include a methyl group or a phenyl group from an industrial standpoint, and a methyl group is preferable from the standpoint of heat resistance. R 4 is an oxygen atom or a divalent hydrocarbon group. Examples of the divalent hydrocarbon group that is R 4 include alkylene groups such as methylene groups; Alkylene oxyalkylene groups such as ethylene oxyethylene group and ethylene oxypropylene group can be mentioned. Meanwhile, R 4 may be an oxygen atom and is also preferred.
식 중, R5는 독립적으로 수소 원자, 알킬기, 알콕시알킬기 또는 아실기이며, 알킬기인 것이 바람직하고, 표면 처리의 견지에서 특히는 메틸기, 에틸기인 것이 바람직하다. 성분 (G2)는 Si(OR5)로 표시되는 편말단 구조에 의해, 분자 내에 가수 분해성 실릴기를 갖기 때문에, 성분 (C)와 병용한 경우의 표면 처리 효과가 우수하다.In the formula, R 5 is independently a hydrogen atom, an alkyl group, an alkoxyalkyl group, or an acyl group, and is preferably an alkyl group, and is particularly preferably a methyl group or an ethyl group from the viewpoint of surface treatment. Component (G2) has a hydrolyzable silyl group in the molecule due to a single-end structure represented by Si(OR 5 ), and therefore has an excellent surface treatment effect when used in combination with component (C).
식 중의 c는 성분 (G2)의 디오가노실록산 단위의 중합도(말단을 제외한다)이며, 1~250의 정수이고, 1~100의 정수인 것이 바람직하고, 1~50의 정수인 것이 특히 바람직하다. 식 중의 d는 1~3의 정수이며, 바람직하게는 3이다. d가 3인 경우, 성분 (G2)의 편말단은 특히 적합하게는 트리메톡시실릴기(-Si(OMe)3)이다.c in the formula is the degree of polymerization (excluding the terminals) of the diorganosiloxane units of component (G2), and is an integer of 1 to 250, preferably an integer of 1 to 100, and particularly preferably an integer of 1 to 50. d in the formula is an integer of 1 to 3, and is preferably 3. When d is 3, one terminal of component (G2) is particularly preferably a trimethoxysilyl group (-Si(OMe) 3 ).
성분 (G)의 배합량(성분 (G1)과 성분 (G2)를 병용하는 경우에는 그 총량)은 성분 (C)의 표면 처리에 충분한 양이면 특별히 제한되는 것은 아니지만, 일 예로서, 조성물 전체에서의 성분 (A) 100 질량부에 대하여 0.005~100 질량부의 범위 내이며, 0.05~100 질량부인 것이 바람직하고, 0.5~50 질량부인 것이 더욱 바람직하다.The amount of component (G) (the total amount when component (G1) and component (G2) are used together) is not particularly limited as long as it is sufficient for surface treatment of component (C), but as an example, it may be used in the entire composition. It is within the range of 0.005 to 100 parts by mass, preferably 0.05 to 100 parts by mass, and more preferably 0.5 to 50 parts by mass, based on 100 parts by mass of component (A).
[(H) C6 이상의 알킬알콕시실란 또는 그의 가수 분해 축합물][(H) C6 or higher alkylalkoxysilane or hydrolyzed condensate thereof]
성분 (H)는 성분 (G)와 마찬가지로, 조성물 중에서 성분 (C)인 열전도성 충전제의 표면 처리제로서 기능하는 성분이며, 성분 (C)의 배합량을 개선하면서, 조성물 전체의 점도 및 유동성을 개선하며, 또한 접착 특성을 개선하는 성분이다. 이러한 알콕시실란은 C6 이상의 알킬기를 가질 필요가 있으며, 메틸기 등의 C6 미만의 알킬기만을 포함하는 알킬알콕시실란 또는 그의 가수 분해 축합물을 사용한 경우, 설령 성분 (G), 후술하는 성분 (I) 중 접착 부여제를 병용하더라도 충분한 접착 특성을 실현할 수 없는 경우가 있다.Component (H), like component (G), is a component that functions as a surface treatment agent for the thermally conductive filler of component (C) in the composition, and improves the viscosity and fluidity of the entire composition while improving the amount of component (C). , It is also an ingredient that improves adhesive properties. These alkoxysilanes must have an alkyl group of C6 or more, and when an alkylalkoxysilane containing only alkyl groups of less than C6, such as a methyl group, or a hydrolyzed condensate thereof is used, even if one of component (G) or component (I) described later is used, adhesive Even if an imparting agent is used in combination, there are cases where sufficient adhesive properties cannot be achieved.
탄소 원자수 6 이상의 알킬기의 구체적인 예로서는 헥실기, 옥틸기, 도데실기, 테트라데실기, 헥사데실기, 옥타데실기 등의 알킬기나 벤질기, 페닐에틸기 등의 아르알킬기 등을 열거할 수 있으나, 특히 탄소수 6~20의 알킬기가 바람직하다.Specific examples of alkyl groups having 6 or more carbon atoms include alkyl groups such as hexyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group, and octadecyl group, and aralkyl groups such as benzyl group and phenylethyl group. In particular, An alkyl group having 6 to 20 carbon atoms is preferred.
적합하게는, 성분 (H)는 하기 구조식:Suitably, component (H) has the structural formula:
YnSi(OR)4-n Y n Si(OR) 4-n
(식 중, Y는 탄소 원자수 6~18의 알킬기이고, R은 탄소 원자수 1~5의 알킬기이고, n는 1~3의 수이다)(In the formula, Y is an alkyl group with 6 to 18 carbon atoms, R is an alkyl group with 1 to 5 carbon atoms, and n is a number from 1 to 3.)
으로 표시되는 알콕시실란이며, OR기로서 메톡시기, 에톡시기, 프로폭시기, 부톡시기 등이 예시되고, 특히 메톡시기 및 에톡시기가 바람직하다. 아울러, n은 1, 2 또는 3이며, 특히 1인 것이 바람직하다.It is an alkoxysilane represented by , and examples of the OR group include methoxy group, ethoxy group, propoxy group, butoxy group, etc., and methoxy group and ethoxy group are particularly preferable. In addition, n is 1, 2 or 3, and is especially preferably 1.
이러한 성분 (E1)은 구체적으로는, C6H13Si(OCH3)3, C8H17Si(OC2H5)3, C10H21Si(OCH3)3, C11H23Si(OCH3)3, C12H25Si(OCH3)3, C14H29Si(OC2H5)3 등이 예시되고, 가장 적합하게는 데실트리메톡시실란이다.These components (E1) are specifically, C 6 H 13 Si(OCH 3 ) 3 , C 8 H 17 Si(OC 2 H 5 ) 3 , C 10 H 21 Si(OCH 3 ) 3 , C 11 H 23 Si. (OCH 3 ) 3 , C 12 H 25 Si(OCH 3 ) 3 , C 14 H 29 Si(OC 2 H 5 ) 3, etc. are exemplified, and the most suitable one is decyltrimethoxysilane.
성분 (H)의 배합량은 성분 (C)의 표면 처리에 충분한 양이면 특별히 제한되는 것은 아니지만, 일 예로서, 조성물 전체에서의 성분 (A) 100 질량부에 대하여 0.005~20 질량부의 범위 내이며, 0.05~10 질량부인 것이 바람직하고, 0.5~7.5 질량부인 것이 더욱 바람직하다.The amount of component (H) is not particularly limited as long as it is sufficient for surface treatment of component (C), but as an example, it is within the range of 0.005 to 20 parts by mass with respect to 100 parts by mass of component (A) in the entire composition, It is preferably 0.05 to 10 parts by mass, and more preferably 0.5 to 7.5 parts by mass.
[(I) 하이드로실릴화 반응 억제제, 접착 촉진제, 유기 용제 및 그 외 첨가제][(I) Hydrosilylation reaction inhibitors, adhesion promoters, organic solvents and other additives]
본 발명에 관한 조성물은 성분 (A)~(F)를 필수로 하고, 임의로 성분 (C)의 표면 처리제로서 성분 (G) 및/또는 성분 (H)를 포함할 수도 있는 동시에, 이하의 그 외 성분을 포함할 수 있다.The composition according to the present invention essentially contains components (A) to (F), and may optionally contain component (G) and/or component (H) as a surface treatment agent for component (C), as well as other components as described below. May contain ingredients.
[하이드로실릴화 반응 억제제][Hydrosilylation reaction inhibitor]
본 발명의 조성물에는 그의 취급 작업성의 견지에서, 추가로 하이드로실릴화 반응 억제제를 포함하는 것이 바람직하다. 하이드로실릴화 반응 억제제는 본 발명의 경화성 오가노폴리실록산 조성물의 하이드로실릴화 반응을 억제하기 위한 성분이며, 구체적으로는 예를 들어, 에티닐사이클로헥산올과 같은 아세틸렌계, 아민계, 카복실산 에스테르계, 아인산 에스테르계 등의 반응 억제제를 들 수 있다. 반응 억제제의 첨가량은 통상 경화성 오가노폴리실록산 조성물 전체의 0.001~5질량%이다. 특히, 본 조성물의 취급 작업성을 향상시키는 목적으로는, 3-메틸-1-부틴-3-올, 3,5-디메틸-1-헥신-3-올, 3-페닐-1-부틴-3-올(=페닐부틴올) 등의 아세틸렌계 화합물; 3-메틸-3-펜텐-1-인, 3,5-디메틸-3-헥센-1-인 등의 엔인 화합물; 1,3,5,7-테트라메틸-1,3,5,7-테트라비닐사이클로테트라실록산, 1,3,5,7-테트라메틸-1,3,5,7-테트라헥세닐사이클로테트라실록산 등의 사이클로알케닐실록산; 벤조트리아졸 등의 트리아졸 화합물 등을 특별히 제한없이 사용할 수 있다.From the viewpoint of handling operability, the composition of the present invention preferably further contains a hydrosilylation reaction inhibitor. The hydrosilylation reaction inhibitor is a component for suppressing the hydrosilylation reaction of the curable organopolysiloxane composition of the present invention, and specifically includes, for example, acetylene-based, amine-based, carboxylic acid ester-based substances such as ethynylcyclohexanol, Reaction inhibitors, such as a phosphorous acid ester type, can be mentioned. The addition amount of the reaction inhibitor is usually 0.001 to 5% by mass of the total curable organopolysiloxane composition. In particular, for the purpose of improving the handling properties of the present composition, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-phenyl-1-butyn-3 Acetylene-based compounds such as -ol (=phenylbutinol); Enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane Cycloalkenylsiloxanes such as; Triazole compounds such as benzotriazole can be used without particular limitation.
[접착 부여제][Adhesion imparting agent]
본 발명의 조성물에는 그의 경화물의 접착 강도 및 기재에 대한 영구 접착성을 개선하는 목적으로, 추가로 접착 부여제를 배합할 수도 있다. 본 발명에서 사용 가능한 접착 부여제는 종래 공지의 접착 부여제인 아미노기 함유 오가노알콕시실란과 에폭시기 함유 오가노알콕시실란의 반응 혼합물(특정 구조를 갖는 카바실라트란 유도체, 실라트란 유도체를 포함한다), 디실라알칸 화합물(예를 들어, 1, 6-비스(트리메톡시실릴)헥산)로 대표되는 알콕시실릴기를 분자 중에 2개 이상 갖는 유기 화합물, 에폭시기 함유 실란 또는 그 부분 가수 분해 축합물로부터 선택되는 1종류 이상일 수 있으며, 이들 중으로부터 선택되는 2종류 이상의 접착 부여제를 조합하여 사용할 수도 있는 동시에, 바람직하다.An adhesion imparting agent may be further added to the composition of the present invention for the purpose of improving the adhesive strength of the cured product and the permanent adhesion to the substrate. Adhesion imparting agents that can be used in the present invention include reaction mixtures of conventionally known adhesion imparting agents such as amino group-containing organoalkoxysilanes and epoxy group-containing organoalkoxysilanes (including carbacilatrane derivatives and silatrane derivatives having a specific structure), 1 selected from organic compounds having two or more alkoxysilyl groups in the molecule, such as silaalkane compounds (e.g., 1,6-bis(trimethoxysilyl)hexane), epoxy group-containing silanes, or partial hydrolysis condensates thereof There may be more than one type, and two or more types of adhesion imparting agents selected from among these may be used in combination, and it is preferable.
적합하게는, 접착 부여제는Suitably, the adhesion agent is
(IA-1) 일반식:(IA-1) General formula:
Ra nSi(ORb)4-n R a n Si(OR b ) 4-n
(식 중, Ra는 1가의 에폭시기 함유 유기기이고, Rb는 탄소 원자수 1~6의 알킬기 또는 수소 원자이다. n은 1~3의 범위의 수이다)(In the formula, R a is an organic group containing a monovalent epoxy group, and R b is an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. n is a number in the range of 1 to 3.)
으로 표시되는 에폭시기 함유 실란 또는 그의 부분 가수 분해 축합물, 및An epoxy group-containing silane or a partially hydrolyzed condensate thereof, and
(IA-2) 1분자 중에 적어도 2개의 알콕시실릴기를 가지며, 또한 이들 실릴기의 사이에 규소-산소 결합 이외의 결합이 포함되어 있는 유기 화합물(IA-2) An organic compound having at least two alkoxysilyl groups in one molecule and containing bonds other than silicon-oxygen bonds between these silyl groups.
을 5:95~95:5의 질량비, 바람직하게는 50:50~95:5의 질량비, 보다 바람직하게는 60:40~90:30의 질량비로 포함하는 것이다. 아울러, 이들 성분은 단독으로도 오가노폴리실록산 경화물의 초기 접착성을 개선하는 것이지만, 상기 질량비로 병용함으로써, 오가노폴리실록산 경화물의 초기 접착성, 접착 내구성 및 접착 강도(영구 접착성)가 큰폭으로 개선되는 경우가 있다.It is included in a mass ratio of 5:95 to 95:5, preferably in a mass ratio of 50:50 to 95:5, and more preferably in a mass ratio of 60:40 to 90:30. In addition, these components alone improve the initial adhesion of the cured organopolysiloxane, but when used together in the above mass ratio, the initial adhesion, adhesive durability, and adhesive strength (permanent adhesive) of the cured organopolysiloxane are significantly improved. There are cases where it happens.
상기 성분 (IA-1)로서, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필메틸디메톡시실란, 2-(3,4-에폭시사이클로헥실)에틸트리메톡시실란, 2-(3,4-에폭시사이클로헥실)에틸메틸디메톡시실란이 예시된다.As the above component (IA-1), 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl)ethylmethyldimethoxysilane is exemplified.
상기 성분 (IA-2)로서, 1,6-비스(트리메톡시실릴)헥산, 1,6-비스(트리에톡시실릴)헥산, 1,4-비스(트리메톡시실릴)헥산, 1,5-비스(트리메톡시실릴)헥산, 2,5-비스(트리메톡시실릴)헥산, 1-메틸디메톡시실릴-6-트리메톡시실릴헥산, 1-페닐디에톡시실릴-6-트리에톡시실릴헥산, 1,6-비스(메틸디메톡시실릴)헥산 등의 디실라알칸류가 예시된다.As the above component (IA-2), 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,4-bis(trimethoxysilyl)hexane, 1, 5-bis(trimethoxysilyl)hexane, 2,5-bis(trimethoxysilyl)hexane, 1-methyldimethoxysilyl-6-trimethoxysilylhexane, 1-phenyldiethoxysilyl-6-triene Disila alkanes such as toxysilylhexane and 1,6-bis(methyldimethoxysilyl)hexane are exemplified.
상기 성분 (IA-1), (IA-2) 이외의 접착 부여제로서, 일본 공고특허공보 제(소)52-8854호나 일본 공개특허공보 제(평)10-195085호에 개시되어 있는 아미노기 함유 오가노알콕시실란과 에폭시기 함유 오가노알콕시실란의 반응 혼합물(특정 구조를 갖는 카바실라트란 유도체, 실라트란 유도체를 포함한다)을 더 병용할 수도 있다.As an adhesion imparting agent other than the above components (IA-1) and (IA-2), an amino group disclosed in Japanese Patent Application Publication No. 52-8854 or Japanese Patent Application Publication No. 10-195085 A reaction mixture of an organoalkoxysilane and an epoxy group-containing organoalkoxysilane (including carbasilatran derivatives and silatrane derivatives having a specific structure) can also be used in combination.
[유기 용매 그 외 첨가제][Organic solvents and other additives]
본 발명의 경화성 오가노폴리실록산 조성물은 상기한 성분 이외에도, 본 발명의 목적을 해치지 않는 범위에서 임의 성분을 배합할 수 있다. 이 임의 성분으로서는, 예를 들어 규소 원자 결합 수소 원자 및 규소 원자 결합 알케닐기를 함유하지 않는 오가노폴리실록산, 내한성 부여제, 난연성 부여제, 안료, 염료 등을 열거할 수 있다. 또한, 본 발명의 경화성 오가노폴리실록산 조성물은 소망에 따라, 공지의 계면 활성제 등으로 이루어진 1종류 이상의 대전 방지제; 유전성 필러; 전기 전도성 필러; 이형성 성분; 요변성 부여제; 곰팡이 방지제 등을 포함할 수 있다. 또한, 소망에 따라, 유기 용매를 첨가할 수도 있다.In addition to the above-described components, the curable organopolysiloxane composition of the present invention may contain optional components within a range that does not impair the purpose of the present invention. Examples of this optional component include organopolysiloxane containing no silicon atom-bonded hydrogen atom or silicon atom-bonded alkenyl group, cold resistance imparting agent, flame retardancy imparting agent, pigment, dye, etc. Additionally, the curable organopolysiloxane composition of the present invention may optionally contain one or more antistatic agents including known surfactants; hereditary fillers; electrically conductive filler; Release-forming component; thixotropic agent; It may contain anti-fungal agents, etc. Additionally, an organic solvent may be added as desired.
[조성물의 제조 방법 및 제형][Production method and formulation of composition]
본 발명의 경화성 오가노폴리실록산 조성물은 상기 각 성분을 혼합함으로써 조제할 수 있으며, 혼합 장치로서는 성분 (C)의 표면 처리에서 예시한 것과 동일한 장치가 예시된다. 또한, 상기와 같이, 성분 (D)는 성분 (C)의 표면 처리/베이스 히트 후의 타이밍에 첨가할 수도 있고, 성분 (C)의 표면 처리제와 함께 첨가할 수도 있으며, 어느 타이밍에 첨가해도 본 발명의 기술적 효과를 달성 가능하다.The curable organopolysiloxane composition of the present invention can be prepared by mixing the above components, and examples of the mixing device include the same devices as those exemplified for the surface treatment of component (C). In addition, as described above, component (D) may be added at the timing after the surface treatment/base hit of component (C), or may be added together with the surface treatment agent of component (C), and the present invention can be added at any timing. It is possible to achieve technical effects.
보다 구체적으로는, 본 발명에 관한 조성물은More specifically, the composition according to the present invention is
i) 상기 성분 (A), 성분 (C), 및 임의로 성분 (G) 및/또는 성분 (H)를 혼합 후, 당해 혼합물을 가열 혼합하는 공정 후, 성분 (D) 및 그 외 성분을 혼합하는 공정을 갖는 제조 방법;i) After mixing the component (A), component (C), and optionally component (G) and/or component (H), mixing the mixture with heat, followed by mixing component (D) and other components. Manufacturing method with process;
ii) 상기 성분 (A), 성분 (C), 성분 (D), 및 임의로 성분 (G) 및/또는 성분 (H)를 혼합 후, 당해 혼합물을 가열 혼합하는 공정 후, 그 외 성분을 혼합하는 공정을 갖는 제조 방법ii) After mixing the component (A), component (C), component (D), and optionally component (G) and/or component (H), mixing the other components after the step of heating and mixing the mixture. Manufacturing method with process
중 어느 제조 방법(혼합 프로세스)에 의해 제조하는 것이 바람직하다. 아울러, 가열 조건은 앞서 성분 (C)의 표면 처리에서 설명한 베이스 히트 조건과 동일하며, 혼합 시에는 전체가 실질적으로 균일하게 되도록 혼합하는 것이 바람직하다.It is preferable to manufacture by any of the manufacturing methods (mixing process). In addition, the heating conditions are the same as the base heat conditions previously described in the surface treatment of component (C), and it is preferable to mix so that the entire mixture is substantially uniform.
본 발명에 관한 경화성 오가노폴리실록산 조성물은 1액형의 조성물, 적합하게는 상기 하이드로실릴화 반응 억제제 및 그 외 성분을 포함하는 조성물일 수도 있으며, 개별적으로 보존되는 2종류 이상의 조성물로 이루어진 다성분형 조성물일 수도 있다. 다성분형 조성물의 경우, 상기 성분 (A), 성분 (B) 성분 및 성분 (E)를 동시에 포함하지 않는 것이 필요하다. 이는, 이들 성분(주제, 가교제 및 촉매)을 동시에 배합하면 가교 반응이 자발적으로 시작되어, 당해 조성물의 저장 안정성이 단기간에 없어져, 다성분형 조성물의 목적인 장기에 걸친 저장 안정성 및 취급 작업성을 실현할 수 없게 되는 경우가 있다. 아울러, 다성분형 조성물은 사용 시에 공통 용기 중에서 믹서 등의 기계력을 이용하여 교반하거나, 다성분의 혼합에 대응한 디스펜서 등을 이용해 혼합되어 도포 내지 적용된다.The curable organopolysiloxane composition according to the present invention may be a one-component composition, suitably a composition containing the hydrosilylation reaction inhibitor and other components, and may be a multi-component composition consisting of two or more types of compositions that are individually preserved. It may be. In the case of a multi-component composition, it is necessary not to contain the above components (A), (B), and (E) at the same time. This means that when these components (main agent, cross-linking agent, and catalyst) are mixed at the same time, the cross-linking reaction starts spontaneously, and the storage stability of the composition is lost in a short period of time, making it impossible to realize the long-term storage stability and handling workability that are the goals of a multi-component composition. There are times when it becomes impossible. In addition, when the multi-component composition is used, it is applied or applied by stirring it in a common container using mechanical force such as a mixer, or mixing it using a dispenser suitable for mixing multiple components.
[경화성][Hardability]
본 발명에 관한 경화성 오가노폴리실록산 조성물은 하이드로실릴화 반응에 의해 경화하여, 열전도성이 우수하며, 또한 가열 에이징 후에도 경도 변화가 억제되고, 유연성 및 응력 완화 특성이 우수한 오가노폴리실록산 경화물을 형성한다. 이 하이드로실릴화 반응 경화형의 실리콘 조성물을 경화하기 위한 온도 조건은 특별히 한정되지 않으나, 통상 20℃~200℃의 범위 내, 바람직하게는 20℃~150℃의 범위 내이며, 보다 바람직하게는 20~80℃의 범위 내이다. 소망에 따라, 고온 단시간에 경화시킬 수도 있고, 실온 등의 저온에서 장시간(예를 들어 수시간~수일)에 걸쳐 경화시킬 수도 있으며, 특별히 제한되는 것은 아니다. 아울러, 성분 (E)의 적어도 일부에 고에너지선 활성화 촉매 또는 광활성화 촉매를 선택함으로써, 고에너지선의 조사를 트리거로 하는 경화를 수행할 수도 있다.The curable organopolysiloxane composition according to the present invention is cured by a hydrosilylation reaction to form a cured organopolysiloxane that has excellent thermal conductivity, suppresses changes in hardness even after heat aging, and has excellent flexibility and stress relaxation properties. . The temperature conditions for curing this hydrosilylation reaction-curable silicone composition are not particularly limited, but are usually within the range of 20°C to 200°C, preferably within the range of 20°C to 150°C, and more preferably within the range of 20°C to 200°C. It is within the range of 80℃. Depending on desire, it may be cured at a high temperature for a short period of time, or at a low temperature such as room temperature over a long period of time (for example, several hours to several days), but there is no particular limitation. In addition, by selecting a high-energy ray-activated catalyst or a photo-activated catalyst for at least part of the component (E), curing can be performed by irradiation of high-energy rays as a trigger.
본 발명에 관한 경화성 오가노폴리실록산 조성물을 이용함으로써, 방열 부품 또는 당해 방열 부품을 탑재한 회로 기판에 상기 경화성 오가노폴리실록산 조성물을 적용하고, 20℃~150℃, 바람직하게는 130℃미만, 예를 들어 20~125℃의 범위에서 경화물을 형성시켜, 방열 부재를 마련하여 이루어진 방열 구조체를 얻을 수 있다.By using the curable organopolysiloxane composition according to the present invention, the curable organopolysiloxane composition is applied to a heat dissipation component or a circuit board mounted with the heat dissipation component, and the temperature is 20°C to 150°C, preferably less than 130°C, for example. For example, a heat dissipation structure can be obtained by forming a cured product in the range of 20 to 125°C and providing a heat dissipation member.
[열전도율][Thermal conductivity]
본 발명의 경화성 오가노폴리실록산 조성물은 열전도성 충전제를 안정적으로 고충전할 수 있으며, 2.5 W/mK 이상, 적합하게는 3.0 W/mK 이상, 보다 적합하게는 7.0 W/mK 이상의 열전도율을 구비한다. 아울러, 본 발명의 경화성 오가노폴리실록산 조성물에서는, 열전도율이 2.5~9.5 W/mK, 소망에 따라 열전도율이 7.0~9.5 W/mK인 조성물 및 경화물을 설계 가능하며, 또한 가열 에이징 후에도 경도 변화가 억제되고, 유연성 및 응력 완화 특성이 우수한 열전도성 경화물을 실현 가능하다.The curable organopolysiloxane composition of the present invention can stably and highly charge a thermally conductive filler, and has a thermal conductivity of 2.5 W/mK or higher, preferably 3.0 W/mK or higher, and more preferably 7.0 W/mK or higher. In addition, in the curable organopolysiloxane composition of the present invention, it is possible to design compositions and cured products with a thermal conductivity of 2.5 to 9.5 W/mK, and if desired, a thermal conductivity of 7.0 to 9.5 W/mK, and hardness change is suppressed even after heat aging. It is possible to realize a thermally conductive cured material with excellent flexibility and stress relief properties.
[용도 및 방열 구조체][Use and heat dissipation structure]
본 발명의 경화성 오가노폴리실록산 조성물 및 그의 경화물은 열전도에 의한 발열성 부품의 냉각을 위해, 발열성 부품의 열경계면과 히트 싱크 또는 회로 기판 등의 방열 부재의 계면에 개재시키는 열전달 재료(열전도성 부재)로서 유용하며, 이를 구비한 방열 구조체를 형성할 수 있다. 여기서, 발열성 부품의 종류나 크기, 세부 구조는 특별히 한정되는 것은 아니지만, 본 발명의 경화성 오가노폴리실록산 조성물을 경화시켜 이루어진 경화물은 높은 열전도성을 가지면서, 부재에 대한 초기 접착성 및 접착 강도가 우수할 뿐만 아니라, 가열 에이징 후에도 장기간에 걸쳐 경도 변화가 억제되고, 유연성 및 응력 완화 특성을 유지할 수 있기 때문에, 진동 등으로 발열성 부재로부터 박락이나 공극을 발생시키기 어렵고, 밀착성과 추종성이 높고, 또한 공업적 생산성이 우수하기 때문에, 자동차 부품, 전기·전자 부품 또는 셀 방식의 이차전지류를 포함하는 전기·전자 기기의 방열 구조체에 적합하게 적용된다.The curable organopolysiloxane composition of the present invention and its cured product are heat transfer materials (thermal conductivity) interposed between the thermal interface of the heat-generating part and the interface of a heat-dissipating member such as a heat sink or circuit board in order to cool the heat-generating part by heat conduction. member), and a heat dissipation structure equipped with it can be formed. Here, the type, size, and detailed structure of the heat-generating part are not particularly limited, but the cured product obtained by curing the curable organopolysiloxane composition of the present invention has high thermal conductivity, initial adhesion to the member, and adhesive strength. Not only is it excellent, but hardness changes are suppressed over a long period of time even after heat aging, and flexibility and stress relaxation characteristics can be maintained. Therefore, it is difficult to generate peeling or voids from the exothermic member due to vibration, etc., and adhesion and followability are high. In addition, because it has excellent industrial productivity, it is suitably applied to heat dissipation structures of electrical and electronic devices including automobile parts, electrical and electronic components, or cell-type secondary batteries.
이러한 방열 구조체의 구조는 특별히 제한되는 것은 아니지만, 방열 부품 또는 당해 방열 부품을 탑재한 회로 기판에 상기 경화성 오가노폴리실록산 조성물 또는 그의 경화물을 개재하여 방열 부재를 마련하여 이루어진 방열 구조체를 예시할 수 있다. 이러한 구조는, 예를 들어 방열성 부품인 전자 부품이 회로 기판 위에 탑재되어, 당해 전자 부품으로부터 발생하는 열을 경화성 오가노폴리실록산 조성물 또는 그의 경화물의 박막층을 개재하여 방열 부재에서 방열하는 구조가 예시되며, 이들 부재는 본 발명의 특징인 가열 에이징 후의 경도 변화가 작고, 방열 부재의 유연성, 응력 완화성을 유지하며, 밀착성과 추종성이 우수하기 때문에, 수평면뿐만 아니라 경사면 내지 수직면에도 적합하게 배치될 수도 있다.The structure of this heat dissipation structure is not particularly limited, but a heat dissipation structure formed by providing a heat dissipation member through the curable organopolysiloxane composition or a cured product thereof on a heat dissipation component or a circuit board on which the heat dissipation component is mounted can be exemplified. . This structure is exemplified by, for example, a structure in which an electronic component that is a heat dissipating component is mounted on a circuit board, and heat generated from the electronic component is dissipated by a heat dissipating member through a thin film layer of a curable organopolysiloxane composition or a cured product thereof, Since these members have a small change in hardness after heat aging, which is a feature of the present invention, maintain the flexibility and stress relief properties of the heat radiation member, and have excellent adhesion and followability, they can be appropriately placed not only on horizontal surfaces but also on inclined or vertical surfaces.
이러한 방열 구조체에 있어서, 경화성 오가노폴리실록산 조성물 또는 그의 경화물의 두께는 특별히 한정되지 않으나, 0.1~100 mm의 범위일 수 있으며, 당해 조성물 또는 그의 경화물이 간극 없이 충전된 전자 부품으로부터 발생하는 열을 방열 부재에 효율적으로 전달할 수 있다.In this heat dissipation structure, the thickness of the curable organopolysiloxane composition or its cured product is not particularly limited, but may range from 0.1 to 100 mm, and the composition or its cured product dissipates heat generated from electronic components filled without gaps. It can be efficiently transmitted to the heat dissipation member.
상기 열전도성 실리콘 조성물로 이루어진 부재를 구비한 전기·전자 기기는 특별히 제한되는 것은 아니지만, 예를 들어 셀 방식의 리튬 이온 전극 이차전지, 셀 스택식의 연료 전지 등의 이차전지; 프린트 기판과 같은 전자 회로 기판; 다이오드(LED), 유기 전계 소자(유기 EL), 레이저 다이오드, LED 어레이와 같은 광반도체 소자가 패키지된 IC칩; 퍼스널 컴퓨터, 디지털 비디오 디스크, 휴대 전화, 스마트 폰 등의 전자 기기에 사용되는 CPU; 드라이버 IC나 메모리 등의 LSI 칩 등이 예시된다. 특히, 고집적 밀도로 형성된 고성능 디지털·스위칭 회로에서는, 집적 회로의 성능 및 신뢰성에 대해 열 제거(방열)가 주요한 요소가 되고 있는데, 본 발명에 관한 경화성 오가노폴리실록산 조성물을 이용하여 이루어진 열전도성 부재는 수송기 중의 엔진 제어나 파워·트레인계, 에어컨 제어 등의 파워 반도체 용도에 적용한 경우에도 방열성 및 취급 작업성이 우수하며, 전자 제어 유닛(ECU) 등 차량 탑재 전자 부품에 편입되어 가혹한 환경하에서 사용된 경우에도 부재와의 견고한 접착력을 유지하고, 우수한 내열성 및 열전도성을 실현할 수 있다.Electrical and electronic devices including members made of the thermally conductive silicone composition are not particularly limited, and examples include secondary batteries such as cell-type lithium ion electrode secondary batteries and cell-stack type fuel cells; Electronic circuit boards, such as printed boards; IC chips packaged with optical semiconductor elements such as diodes (LEDs), organic electric field elements (organic ELs), laser diodes, and LED arrays; CPUs used in electronic devices such as personal computers, digital video discs, mobile phones, and smart phones; Examples include LSI chips such as driver ICs and memory. In particular, in high-performance digital switching circuits formed at high integration density, heat removal (heat dissipation) is a major factor in the performance and reliability of the integrated circuit, and the thermally conductive member made using the curable organopolysiloxane composition according to the present invention is It has excellent heat dissipation and handling properties even when applied to power semiconductor applications such as engine control, power/train system, and air conditioner control in transport aircraft, and when incorporated into vehicle-mounted electronic components such as electronic control units (ECU) and used under harsh environments. It is possible to maintain strong adhesion to the material and realize excellent heat resistance and thermal conductivity.
실시예Example
이하, 본 발명에 관해 실시예를 들어 설명하지만, 본 발명이 이들에 의해 한정되는 것은 아니다. 이하에 나타내는 실시예 및 비교예에서는 하기 화합물 내지 조성물을 원료로 사용했다.Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto. In the examples and comparative examples shown below, the following compounds and compositions were used as raw materials.
[조성물의 조제 및 열전도성 실리콘 경화물(평가 샘플)의 제작][Preparation of composition and production of heat conductive silicone cured material (evaluation sample)]
각 성분을 후술하는 방법으로 혼합하여, 실시예 1~12 및 비교예 1~6의 경화성 오가노폴리실록산 조성물(이하, 「열전도성 실리콘 조성물」이라고 하는 경우가 있다)을 얻었다. 그 후, 각각의 열전도성 실리콘 조성물을 높이 6 mm, 세로 50 mm, 가로 30 mm의 금형에 충전하고, 50℃에서 30분에 걸쳐 경화시킨 후, 금형으로부터 꺼내 열전도성 실리콘 경화물을 얻었다. 얻어진 열전도성 실리콘 경화물의 열전도율, 경도 및 가열 에이징 후의 경도 변화는 이하의 방법으로 측정했다.Each component was mixed by the method described later to obtain the curable organopolysiloxane composition of Examples 1 to 12 and Comparative Examples 1 to 6 (hereinafter sometimes referred to as “thermal conductive silicone composition”). After that, each heat conductive silicone composition was filled into a mold with a height of 6 mm, a length of 50 mm, and a width of 30 mm, and the mold was cured at 50°C for 30 minutes, and then taken out from the mold to obtain a heat conductive silicone cured product. The thermal conductivity, hardness, and change in hardness after heat aging of the obtained thermally conductive silicone cured product were measured by the following methods.
[열전 전도율][Thermoelectric conductivity]
열전도율의 측정은 상기 조건으로 얻어진 열전도성 실리콘 경화물을 2매 이용하여, 교토덴시코교 가부시키가이샤(KYOTO ELECTRONICS MANUFACTURING CO., LTD.) 제품 TPS-500(핫 디스크법)에 의해 측정했다.Thermal conductivity was measured by TPS-500 (hot disk method) manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD. using two sheets of thermally conductive silicone cured material obtained under the above conditions.
[경도(타입 E 경도)][Hardness (Type E hardness)]
경도의 측정은 상기 조건으로 얻어진 열전도성 실리콘 경화물을 2매 겹쳐, ASKER사 제품 ASKER TYPE E형 경도계를 사용하여 3초 후의 값을 측정했다.The hardness was measured by stacking two sheets of the heat conductive silicone cured product obtained under the above conditions and measuring the value after 3 seconds using an ASKER TYPE E hardness tester manufactured by ASKER.
[경도 변화][Hardness change]
상기 조건으로 얻어진 열전도성 실리콘 경화물 2매를 150℃의 열풍 순환식 오븐 중에서 100시간 양생했다. 꺼낸 후, 25℃까지 냉각한 후, 열전도성 실리콘 경화물을 2매 겹쳐, ASKER사 제품 ASKER TYPE E형 경도계를 사용하여 3초 후의 값을 측정했다. 양생 전과 150℃ 양생 후의 경도의 차를 측정했다.Two sheets of heat conductive silicone cured material obtained under the above conditions were cured for 100 hours in a hot air circulation oven at 150°C. After taking it out and cooling it to 25°C, two sheets of heat conductive silicone cured material were overlapped, and the value after 3 seconds was measured using an ASKER TYPE E hardness tester manufactured by ASKER. The difference in hardness before curing and after curing at 150°C was measured.
본 발명 조성물은 이하의 각 성분에 의해 형성되어 있다.The composition of the present invention is formed of the following components.
성분 (A):Component (A):
A-1: 분자쇄 양말단 디메틸비닐실록시기 봉쇄 디메틸폴리실록산(점도 60 mPa·s, Vi 함유량 1.52질량%)A-1: Dimethylpolysiloxane with dimethylvinylsiloxy groups blocked at both ends of the molecular chain (viscosity 60 mPa·s, Vi content 1.52% by mass)
A-2: 분자쇄 양말단 디메틸비닐실록시기 봉쇄 디메틸폴리실록산(점도 400 mPa·s, Vi 함유량 0.43질량%)A-2: Dimethylpolysiloxane with dimethylvinylsiloxy groups blocked at both ends of the molecular chain (viscosity 400 mPa·s, Vi content 0.43% by mass)
성분 (B):Component (B):
B-1: 분자쇄 양말단 트리메틸실록시기 봉쇄 메틸하이드로겐실록산·디메틸실록산 공중합체, 분자 내에 평균 2개, 분자쇄 측쇄에 평균 2개(점도 20 mPa·s, Si-H 함유량 0.10질량%)B-1: Methylhydrogensiloxane/dimethylsiloxane copolymer with blocked trimethylsiloxy groups at both ends of the molecular chain, an average of 2 in the molecule and an average of 2 in the side chain of the molecular chain (viscosity 20 mPa·s, Si-H content 0.10% by mass)
B-2: 분자쇄 양말단 트리메틸실록시기 봉쇄 메틸하이드로겐실록산·디메틸실록산 공중합체, 분자 내에 평균 5개, 분자쇄 측쇄에 평균 5개(점도 5 mPa·s, Si-H 함유량 0.75질량%)B-2: Methylhydrogensiloxane/dimethylsiloxane copolymer with blocked trimethylsiloxy groups at both ends of the molecular chain, with an average of 5 in the molecule and 5 on average in the side chains of the molecular chain (viscosity 5 mPa·s, Si-H content 0.75% by mass)
B-3: 1,1,1,3,5,5,5-헵타메틸트리실록산(Si-H 함유량 0.45질량%)B-3: 1,1,1,3,5,5,5-heptamethyltrisiloxane (Si-H content 0.45% by mass)
성분 (C):Component (C):
C-1: 평균 입경 0.5 μm의 다면체 구상 α형 산화알루미늄 분말(스미토모카가쿠 가부시키가이샤(Sumitomo Chemical Company, Limited) 제품, AA04)C-1: Polyhedral spherical α-type aluminum oxide powder with an average particle diameter of 0.5 μm (AA04, manufactured by Sumitomo Chemical Company, Limited)
C-2: 평균 입경 2 μm의 다면체 구상 α형 산화알루미늄 분말(스미토모카가쿠 가부시키가이샤 제품, AA2)C-2: Polyhedral spherical α-type aluminum oxide powder with an average particle diameter of 2 μm (Sumitomo Chemical Co., Ltd. product, AA2)
C-3: 평균 입경 0.4 μm의 파쇄상 산화알루미늄 분말(스미토모카가쿠 가부시키가이샤 제품, AES-12)C-3: Crushed aluminum oxide powder with an average particle size of 0.4 μm (Sumitomo Chemical Co., Ltd. product, AES-12)
C-4: 평균 입경 2.5 μm의 파쇄상 산화알루미늄 분말(스미토모카가쿠 가부시키가이샤 제품, AL-M73A)C-4: Crushed aluminum oxide powder with an average particle size of 2.5 μm (Sumitomo Chemical Co., Ltd. product, AL-M73A)
C-5: 평균 입경 95 μm의 구상 용융 고화 산화알루미늄 분말(덴카 가부시키가이샤(Denka Company Limited) 제품, DAW-90)C-5: Globular melted solidified aluminum oxide powder with an average particle diameter of 95 μm (DAW-90, manufactured by Denka Company Limited)
C-6: 평균 입자 지름 19 μm의 부정형 질화알루미늄 분말(도요알루미늄 가부시키가이샤(Toyo Aluminium K.K.) 제품, TFZ-S20P)C-6: Amorphous aluminum nitride powder with an average particle diameter of 19 μm (Toyo Aluminum K.K. product, TFZ-S20P)
C-7: 평균 입경 27 μm의 부정형 질화알루미늄 분말(도요알루미늄 가부시키가이샤 제품, TFZ-S30P)C-7: Amorphous aluminum nitride powder with an average particle diameter of 27 μm (Toyo Aluminum Co., Ltd. product, TFZ-S30P)
C-8: 평균 입경 90 μm의 구상 산화마그네슘 분말C-8: Globular magnesium oxide powder with an average particle diameter of 90 μm
성분 (D):Component (D):
D-1: 스테아르산 칼슘(후지필름 와코쥰야쿠 가부시키가이샤(FUJIFILM Wako Pure Chemical Corporation) 제품)D-1: Calcium stearate (manufactured by FUJIFILM Wako Pure Chemical Corporation)
D-2: 스테아르산(후지필름 와코쥰야쿠 가부시키가이샤 제품)D-2: Stearic acid (Fujifilm Wako Pure Chemical Industries, Ltd. product)
D-3: 스테아르산 리튬(후지필름 와코쥰야쿠 가부시키가이샤 제품)D-3: Lithium stearate (Fujifilm Wako Pure Chemical Industries, Ltd. product)
성분 (E):Ingredient (E):
E-1: 백금 농도가 0.6중량%인 백금과 1, 3-디비닐-1, 1, 3, 3-테트라메틸디실록산의 착체E-1: Complex of platinum and 1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane with a platinum concentration of 0.6% by weight
성분 (F):Component (F):
F-1: 29H, 31H-프탈로시아니나토(2-)-N29, N30, N31, N32 구리F-1: 29H, 31H-phthalocyanato(2-)-N29, N30, N31, N32 copper
경화 지연제: 페닐부틴올Cure retarder: Phenylbutinol
성분 (G1):Ingredient (G1):
필러 처리제 (1): 식: (CH3)3SiO[(CH3)2SiO]30Si(OCH3)3 Filler treatment agent (1): Formula: (CH 3 ) 3 SiO[(CH 3 ) 2 SiO] 30 Si(OCH 3 ) 3
으로 표시되는 오가노폴리실록산Organopolysiloxane represented by
성분 (H):Component (H):
필러 처리제 (2): 데실트리메톡시실란Filler treatment agent (2): Decyltrimethoxysilane
[실시예 1][Example 1]
성분 (A-1) 100 질량부, 성분 (F-1) 1.33 질량부를 계량하고, 거기에 60분에 걸쳐 성분 (C-1) 128 질량부, 성분 (C-2) 180 질량부, 성분 (C-5) 317.5 질량부, 성분 (C-6) 66.4 질량부, 성분 (C-7) 161 질량부를 순차 혼합했다. 균일하게 한 후, 감압하에서 160℃에서 60분 가열 혼합 후, 실온까지 냉각하여 혼합물을 얻었다.Weigh 100 parts by mass of component (A-1) and 1.33 parts by mass of component (F-1), and add 128 parts by mass of component (C-1), 180 parts by mass of component (C-2), and component ( C-5) 317.5 parts by mass, 66.4 parts by mass of component (C-6), and 161 parts by mass of component (C-7) were sequentially mixed. After uniformity, the mixture was obtained by heating and mixing at 160°C for 60 minutes under reduced pressure and then cooling to room temperature.
이 혼합물에, 성분 (B-1) 28.4 질량부, 성분 (B-2) 0.28 질량부, 성분 (D-1) 0.95 질량부, 반응 억제제로서 페닐부틴올 0.016 질량부를 균일 혼합했다. 그 후, 성분 (E-1) 0.66 질량부를 균일 혼합하여, 열전도성 실리콘 조성물을 얻었다. 아울러, 본 발명에서의 각 실시예/비교예에서의 혼합에는 TOKUSHU KIKA KOGYO CO., LTD. 제품 T.K.HIVIS MIX(모델 번호)를 혼합 장치로서 사용했다.Into this mixture, 28.4 parts by mass of component (B-1), 0.28 parts by mass of component (B-2), 0.95 parts by mass of component (D-1), and 0.016 parts by mass of phenylbutinol as a reaction inhibitor were uniformly mixed. After that, 0.66 parts by mass of component (E-1) was uniformly mixed to obtain a thermally conductive silicone composition. In addition, the mixing in each Example/Comparative Example of the present invention includes TOKUSHU KIKA KOGYO CO., LTD. The product T.K.HIVIS MIX (model number) was used as a mixing device.
[실시예 2][Example 2]
실시예 1의 성분 (D-1) 0.95 질량부를 성분 (D-2) 0.95 질량부로 치환한 것 이외에는 실시예 1과 동일하게 열전도성 실리콘 조성물을 얻었다.A thermally conductive silicone composition was obtained in the same manner as in Example 1, except that 0.95 parts by mass of the component (D-1) in Example 1 was replaced with 0.95 parts by mass of the component (D-2).
[비교예 1][Comparative Example 1]
실시예 1로부터 성분 (D-1) 0.95 질량부를 제외한 것 이외에는 실시예 1과 동일하게 열전도성 실리콘 조성물을 얻었다.A thermally conductive silicone composition was obtained in the same manner as in Example 1 except that 0.95 parts by mass of component (D-1) was removed from Example 1.
실시예 1, 2 및 비교예 1의 열전도성 실리콘 조성물에 대하여, 조성, 얻어진 열전도성 실리콘 경화물의 열전도율, 경도 및 가열 에이징 후의 경도 변화 등을 표 1에 나타낸다.Regarding the thermally conductive silicone compositions of Examples 1 and 2 and Comparative Example 1, the composition, thermal conductivity, hardness, and change in hardness after heat aging of the obtained cured thermally conductive silicone are shown in Table 1.
[표 1][Table 1]
[실시예 3][Example 3]
성분 (A-1) 100 질량부, 성분 (B-1) 26.4 질량부, 성분 (F-1) 4.8 질량부, 필러 처리제 (1) 41.6 질량부, 필러 처리제 (2) 6.4 질량부를 계량하고, 거기에 60분에 걸쳐 성분 (C-1) 457.6 질량부, 성분 (C-2) 640 질량부, 성분 (C-5) 1120 질량부, 성분 (C-6) 224 질량부, 성분 (C-7) 576 질량부를 순차 혼합했다. 균일하게 한 후, 감압하에서 160℃에서 60분 가열 혼합 후, 실온까지 냉각하여 혼합물을 얻었다.100 parts by mass of component (A-1), 26.4 parts by mass of component (B-1), 4.8 parts by mass of component (F-1), 41.6 parts by mass of filler treatment agent (1), 41.6 parts by mass, filler treatment agent (2) 6.4 parts by mass, In addition, over 60 minutes, 457.6 parts by mass of component (C-1), 640 parts by mass of component (C-2), 1120 parts by mass of component (C-5), 224 parts by mass of component (C-6), and component (C- 7) 576 parts by mass were sequentially mixed. After uniformity, the mixture was obtained by heating and mixing at 160°C for 60 minutes under reduced pressure and then cooling to room temperature.
이 혼합물에, 성분 (B-2) 0.64 질량부, 성분 (D-1) 3.2 질량부, 반응 억제제로서 페닐부틴올 0.053 질량부를 균일 혼합했다. 그 후, 성분 (E-1) 2.4 질량부를 균일 혼합하여, 열전도성 실리콘 조성물을 얻었다.Into this mixture, 0.64 parts by mass of component (B-2), 3.2 parts by mass of component (D-1), and 0.053 parts by mass of phenylbutinol as a reaction inhibitor were uniformly mixed. After that, 2.4 parts by mass of component (E-1) was uniformly mixed to obtain a thermally conductive silicone composition.
[실시예 4][Example 4]
실시예 3의 성분 (D-1) 3.2 질량부를 30.1 질량부로 한 것 이외에는 실시예 3과 동일하게 열전도성 실리콘 조성물을 얻었다.A thermally conductive silicone composition was obtained in the same manner as in Example 3, except that 3.2 parts by mass of the component (D-1) in Example 3 was changed to 30.1 parts by mass.
[실시예 5][Example 5]
실시예 3의 성분 (D-1) 3.2 질량부를 45.1 질량부로 한 것 이외에는 실시예 3과 동일하게 열전도성 실리콘 조성물을 얻었다.A thermally conductive silicone composition was obtained in the same manner as in Example 3, except that 3.2 parts by mass of the component (D-1) in Example 3 was changed to 45.1 parts by mass.
[실시예 6][Example 6]
실시예 3의 성분 (D-1) 3.2 질량부를 60.5 질량부로 한 것 이외에는 실시예 3과 동일하게 열전도성 실리콘 조성물을 얻었다.A thermally conductive silicone composition was obtained in the same manner as in Example 3, except that 3.2 parts by mass of component (D-1) in Example 3 was changed to 60.5 parts by mass.
[실시예 7][Example 7]
성분 (A-1) 100 질량부, 성분 (B-1) 27.4 질량부, 성분 (D-1) 1.61 질량부, 성분 (F-1) 4.8 질량부, 필러 처리제 (1) 40.3 질량부, 필러 처리제 (2) 6.45 질량부를 계량하고, 거기에 60분에 걸쳐 성분 (C-1) 461.3 질량부, 성분 (C-2) 645.2 질량부, 성분 (C-5) 1129 질량부, 성분 (C-6) 225.8 질량부, 성분 (C-7) 580.6 질량부를 순차 혼합했다. 균일하게 한 후, 감압하에서 160℃에서 60분 가열 혼합 후, 실온까지 냉각하여 혼합물을 얻었다.Component (A-1) 100 parts by mass, Component (B-1) 27.4 parts by mass, Component (D-1) 1.61 parts by mass, Component (F-1) 4.8 parts by mass, filler treatment agent (1) 40.3 parts by mass, filler Weigh 6.45 parts by mass of treatment agent (2) and add 461.3 parts by mass of component (C-1), 645.2 parts by mass of component (C-2), 1129 parts by mass of component (C-) over 60 minutes. 6) 225.8 parts by mass and 580.6 parts by mass of component (C-7) were sequentially mixed. After uniformity, the mixture was obtained by heating and mixing at 160°C for 60 minutes under reduced pressure and then cooling to room temperature.
이 혼합물에, 성분 (B-2) 0.65 질량부, 반응 억제제로서 페닐부틴올 0.054 질량부를 균일 혼합했다. 그 후, 성분 (E-1) 2.4 질량부를 균일 혼합하여, 열전도성 실리콘 조성물을 얻었다.Into this mixture, 0.65 parts by mass of component (B-2) and 0.054 parts by mass of phenylbutinol as a reaction inhibitor were uniformly mixed. After that, 2.4 parts by mass of component (E-1) was uniformly mixed to obtain a thermally conductive silicone composition.
[실시예 8][Example 8]
실시예 7의 성분 (D-1) 1.61 질량부를 3.23 질량부로 하고, 필러 처리제 (1) 40.3 질량부를 38.7 질량부로 한 것 이외에는 실시예 7과 동일하게 열전도성 실리콘 조성물을 얻었다.A thermally conductive silicone composition was obtained in the same manner as in Example 7, except that 1.61 parts by mass of the component (D-1) of Example 7 was changed to 3.23 parts by mass, and 40.3 parts by mass of the filler treatment agent (1) was changed to 38.7 parts by mass.
실시예 3~8의 열전도성 실리콘 조성물에 대하여, 조성, 얻어진 열전도성 실리콘 경화물의 열전도율, 경도 및 가열 에이징 후의 경도 변화 등을 표 2에 나타낸다.For the thermally conductive silicone compositions of Examples 3 to 8, the composition, thermal conductivity, hardness, and change in hardness after heat aging of the obtained cured thermally conductive silicone are shown in Table 2.
[표 2][Table 2]
[비교예 2][Comparative Example 2]
실시예 3으로부터 성분 (D-1) 3.20 질량부를 제외한 것 이외에는 실시예 3과 동일하게 열전도성 실리콘 조성물을 얻었다.A thermally conductive silicone composition was obtained in the same manner as in Example 3, except that 3.20 parts by mass of component (D-1) was removed from Example 3.
[비교예 3][Comparative Example 3]
실시예 3의 성분 (D-1) 3.20 질량부를 0.32 질량부로 한 것 이외에는 실시예 3과 동일하게 열전도성 실리콘 조성물을 얻었다.A thermally conductive silicone composition was obtained in the same manner as in Example 3, except that 3.20 parts by mass of the component (D-1) in Example 3 was changed to 0.32 parts by mass.
[비교예 4][Comparative Example 4]
실시예 3의 성분 (D-1) 3.20 질량부를 64 질량부로 한 것 이외에는 실시예 3과 동일하게 열전도성 실리콘 조성물을 얻었다.A thermally conductive silicone composition was obtained in the same manner as in Example 3, except that 3.20 parts by mass of component (D-1) in Example 3 was changed to 64 parts by mass.
비교예 2~4의 열전도성 실리콘 조성물에 대하여, 조성, 얻어진 열전도성 실리콘 경화물의 열전도율, 경도 및 가열 에이징 후의 경도 변화 등을 표 3에 나타낸다.For the thermally conductive silicone compositions of Comparative Examples 2 to 4, the composition, thermal conductivity, hardness, and change in hardness after heat aging of the obtained cured thermally conductive silicone are shown in Table 3.
[표 3][Table 3]
[실시예 9][Example 9]
성분 (A-1) 100 질량부, 성분 (B-1) 25.9 질량부, 성분 (D-1) 3.45 질량부, 성분 (F-1) 5.2 질량부, 필러 처리제 (1) 55.2 질량부, 필러 처리제 (2) 6.9 질량부를 계량하고, 거기에 60분에 걸쳐 성분 (C-1) 500 질량부, 성분 (C-2) 690 질량부, 성분 (C-6) 241 질량부, 성분 (C-7) 621 질량부, 성분 (C-8) 1200 질량부를 순차 혼합했다. 균일하게 한 후, 감압하에서 160℃에서 60분 가열 혼합 후, 실온까지 냉각하여 혼합물을 얻었다.100 parts by mass of component (A-1), 25.9 parts by mass of component (B-1), 3.45 parts by mass of component (D-1), 5.2 parts by mass of component (F-1), 5.2 parts by mass, filler treatment agent (1) 55.2 parts by mass, filler Weigh 6.9 parts by mass of the treatment agent (2), add 500 parts by mass of component (C-1), 690 parts by mass of component (C-2), 241 parts by mass of component (C-6), and component (C-) over 60 minutes. 7) 621 parts by mass and 1200 parts by mass of component (C-8) were sequentially mixed. After uniformity, the mixture was obtained by heating and mixing at 160°C for 60 minutes under reduced pressure and then cooling to room temperature.
이 혼합물에, 성분 (B-2) 0.69 질량부, 반응 억제제로서 페닐부틴올 0.057 질량부를 균일 혼합했다. 그 후, 성분 (E-1) 2.6 질량부를 균일 혼합하여, 열전도성 실리콘 조성물을 얻었다.Into this mixture, 0.69 parts by mass of component (B-2) and 0.057 parts by mass of phenylbutinol as a reaction inhibitor were uniformly mixed. After that, 2.6 parts by mass of component (E-1) was uniformly mixed to obtain a thermally conductive silicone composition.
[실시예 10][Example 10]
실시예 9에 추가로 성분 (B-3) 5.17 질량부를 혼합한 것 이외에는 실시예 9와 동일하게 열전도성 실리콘 조성물을 얻었다.A thermally conductive silicone composition was obtained in the same manner as in Example 9, except that 5.17 parts by mass of component (B-3) was added to Example 9.
[실시예 11][Example 11]
실시예 9의 성분 (D-1) 3.45 질량부를 성분 (D-3) 3.45 질량부로 치환한 것 이외에는 실시예 9와 동일하게 열전도성 실리콘 조성물을 얻었다.A thermally conductive silicone composition was obtained in the same manner as in Example 9, except that 3.45 parts by mass of component (D-1) in Example 9 was replaced with 3.45 parts by mass of component (D-3).
[비교예 5][Comparative Example 5]
실시예 9로부터 성분 (D-1) 3.45 질량부를 제외한 것 이외에는 실시예 9와 동일하게 열전도성 실리콘 조성물을 얻었다.A thermally conductive silicone composition was obtained in the same manner as in Example 9, except that 3.45 parts by mass of component (D-1) was removed from Example 9.
실시예 9~11, 비교예 5의 열전도성 실리콘 조성물에 대하여, 조성, 얻어진 열전도성 실리콘 경화물의 열전도율, 경도 및 가열 에이징 후의 경도 변화 등을 표 4에 나타낸다.For the thermally conductive silicone compositions of Examples 9 to 11 and Comparative Example 5, the composition, thermal conductivity, hardness, and hardness change after heat aging of the obtained cured thermally conductive silicone are shown in Table 4.
[표 4][Table 4]
[실시예 12][Example 12]
성분 (A-2) 100 질량부, 성분 (F-1) 1.8 질량부, 필러 처리제 (2) 5.0 질량부를 계량하고, 거기에 60분에 걸쳐 성분 (C-3) 243 질량부, 성분 (C-4) 540 질량부를 순차 혼합했다. 균일하게 한 후, 감압하에서 160℃에서 60분 가열 혼합 후, 실온까지 냉각하여 혼합물을 얻었다.Weigh out 100 parts by mass of component (A-2), 1.8 parts by mass of component (F-1), and 5.0 parts by mass of filler treatment agent (2), add 243 parts by mass of component (C-3), and component (C) over 60 minutes. -4) 540 parts by mass were sequentially mixed. After uniformity, the mixture was obtained by heating and mixing at 160°C for 60 minutes under reduced pressure and then cooling to room temperature.
이 혼합물에, 성분 (B-1) 8.5 질량부, 성분 (B-2) 0.14 질량부, 성분 (D-1) 0.9 질량부, 반응 억제제로서 페닐부틴올 0.015 질량부를 균일 혼합했다. 그 후, 성분 (E-1) 0.68 질량부를 균일 혼합하여, 열전도성 실리콘 조성물을 얻었다.Into this mixture, 8.5 parts by mass of component (B-1), 0.14 parts by mass of component (B-2), 0.9 parts by mass of component (D-1), and 0.015 parts by mass of phenylbutinol as a reaction inhibitor were uniformly mixed. After that, 0.68 parts by mass of component (E-1) was uniformly mixed to obtain a thermally conductive silicone composition.
[비교예 6][Comparative Example 6]
실시예 12로부터 성분 (D-1) 0.9 질량부를 제외한 것 이외에는 실시예 12와 동일하게 열전도성 실리콘 조성물을 얻었다.A thermally conductive silicone composition was obtained in the same manner as in Example 12, except that 0.9 parts by mass of component (D-1) was removed from Example 12.
실시예 12, 비교예 6의 열전도성 실리콘 조성물에 대하여, 조성, 얻어진 열전도성 실리콘 경화물의 열전도율, 경도 및 가열 에이징 후의 경도 변화 등을 표 5에 나타낸다.For the thermally conductive silicone compositions of Example 12 and Comparative Example 6, the composition, thermal conductivity, hardness, and change in hardness after heat aging of the obtained cured thermally conductive silicone are shown in Table 5.
[표 5][Table 5]
표 1에 나타내는 바와 같이, 성분 (D)를 배합하지 않는 비교예 1은 150℃에서 100시간 양생 후의 경도 변화가 +20인데 반해, 성분 (C) 100 질량부에 대하여 성분 (D)를 0.11 질량부 배합한 실시예 1과 실시예 2의 경도 변화는 각각 +3과 +5이며, 경도 변화가 억제되고 있었다.As shown in Table 1, Comparative Example 1 without component (D) showed a change in hardness of +20 after curing for 100 hours at 150°C, whereas component (D) was added at 0.11 mass parts per 100 mass parts of component (C). The hardness changes of Example 1 and Example 2 that were submixed were +3 and +5, respectively, and the hardness change was suppressed.
표 2에 나타내는 바와 같이, 성분 (D)를 성분 (C) 100 질량부에 대하여 0.05 내지 2 질량부의 범위 내로 배합한 실시예 3~8은 150℃에서 100시간 양생 후의 경도 변화가 +11 내지 +18이었다. 이에 반해, 표 3에 나타내는 바와 같이, 실시예 3으로부터 성분 (D)를 제외한 비교예 2의 경도 변화는 +41이었다. 또한, 실시예 3의 성분 (D)를 성분 (C) 100 질량부에 대하여 0.011 질량부로 한 비교예 3의 경도 변화는 +28이고, 성분 (D)를 2.12 질량부로 한 비교예 4의 경도 변화는 +28이었다. 이로부터, 비교예 2~4에 반해 실시예 3~8에서는 경도 변화가 억제되고 있는 것, 성분 (D)의 배합량이 본 발명의 규정 범위 외(비교예 3, 4)에서는, 경도 변화를 억제할 수 없다는 것을 확인할 수 있어, 양적 한정의 임계적 의의가 나타났다.As shown in Table 2, Examples 3 to 8, in which component (D) was mixed in the range of 0.05 to 2 parts by mass with respect to 100 parts by mass of component (C), had a hardness change of +11 to + after curing for 100 hours at 150°C. It was 18. On the other hand, as shown in Table 3, the change in hardness of Comparative Example 2 excluding component (D) from Example 3 was +41. In addition, the hardness change in Comparative Example 3 in which component (D) of Example 3 was 0.011 parts by mass based on 100 parts by mass of component (C) was +28, and the hardness change in Comparative Example 4 in which component (D) was 2.12 parts by mass. was +28. From this, in contrast to Comparative Examples 2 to 4, the hardness change was suppressed in Examples 3 to 8, and the hardness change was suppressed when the compounding amount of component (D) was outside the specified range of the present invention (Comparative Examples 3 and 4). It was confirmed that this could not be done, revealing the critical significance of quantitative limitation.
표 4에 나타내는 바와 같이, 성분 (D)를 배합하지 않는 비교예 5는 150℃에서 100시간 양생 후의 경도 변화가 +38인데 반해, 성분 (C) 100 질량부에 대하여 성분 (D)를 0.11 질량부 배합한 실시예 9~11에서는 경도 변화가 +11~6이며, 경도 변화가 억제되고 있었다.As shown in Table 4, Comparative Example 5 without component (D) showed a change in hardness of +38 after curing for 100 hours at 150°C, whereas component (D) was added at 0.11 mass parts per 100 mass parts of component (C). In Examples 9 to 11 that were submixed, the hardness change was +11 to +6, and the hardness change was suppressed.
표-5에 나타내는 바와 같이, 성분 (D)를 배합하지 않는 비교예 6은 150℃에서 100시간 양생 후의 경도 변화가 +10인데 반해, 성분 (C) 100 질량부에 대하여 성분 (D)를 0.11 질량부 배합한 실시예 12에서는 경도 변화가 +2이며, 경도 변화가 억제되고 있었다.As shown in Table-5, Comparative Example 6 without component (D) showed a change in hardness of +10 after curing for 100 hours at 150°C, whereas component (D) was added at 0.11 parts per 100 parts by mass of component (C). In Example 12 where the mass parts were mixed, the hardness change was +2, and the hardness change was suppressed.
[총괄][General]
실시예 1~12의 결과로부터, 지방산계 화합물(성분 (D)인 지방산 또는 지방산 금속염)이 무기 필러(혹은 방열 필러) 100 질량부에 대하여 0.05~2 질량부의 범위 내인 경우, 본 조성물은 150℃라는 고온도 조건에서 장기간 에이징한 경우에도 경도 변화가 억제되고 있었다. 이 때문에, 이들 방열 부재는 고온도 조건에서 장기간 사용한 경우에도, 그의 응력 완화 특성이나 유연성이 손상되지 않으며, 충분한 방열 특성을 실현할 수 있는 것으로 기대된다.From the results of Examples 1 to 12, when the fatty acid-based compound (component (D) fatty acid or fatty acid metal salt) is within the range of 0.05 to 2 parts by mass based on 100 parts by mass of the inorganic filler (or heat dissipating filler), the present composition has a temperature of 150°C. Even when aged for a long period of time under high temperature conditions, hardness changes were suppressed. For this reason, even when these heat dissipation members are used for a long period of time under high temperature conditions, their stress relaxation characteristics and flexibility are not impaired and it is expected that sufficient heat dissipation characteristics can be achieved.
한편, 비교예 1~6으로부터, 지방산계 화합물(성분 (D)인 지방산 또는 지방산 금속염)을 배합하지 않는 경우나, 그 배합량이 본 발명의 특허 청구 범위 외인 경우, 이들 비교예에 관한 조성물은 150℃라는 고온도 조건에서 장기간 에이징한 경우, 급격한 경도 변화를 일으켰다. 때문에, 본 발명의 실시예와 달리, 특히 고온에서 장기간 이들 열전도성 부재를 사용한 경우, 경도 변화에 수반하여, 방열체로부터 진동에 의해 물리적으로 박락되거나 간극을 발생시키는 원인이 되어, 당초 예정한 방열 성능을 실현할 수 없게 되는 것이 강하게 염려된다.On the other hand, from Comparative Examples 1 to 6, when the fatty acid-based compound (component (D) fatty acid or fatty acid metal salt) is not blended or when the blended amount is outside the scope of the patent claims of the present invention, the compositions related to these comparative examples have a weight of 150 When aged for a long period of time under high temperature conditions of ℃, a rapid change in hardness occurred. Therefore, unlike the embodiments of the present invention, when these heat conductive members are used for a long period of time, especially at high temperatures, due to changes in hardness, they may be physically separated from the heat radiator due to vibration or cause a gap to be created, thereby dissipating the heat as originally planned. There is a strong concern that performance may not be realized.
Claims (15)
(B) 오가노하이드로겐폴리실록산: 성분 (A)에 포함되는 알케닐기 1몰에 대하여, 성분 (B) 중의 규소 원자 결합 수소 원자가 0.1~10몰이 되는 양,
(C) 열전도성 충전제, 조성물 중의 고형분 전체에 대하여 60~90 부피%의 범위가 되는 양,
(D) 지방산, 지방산 에스테르 및 지방산 금속염으로부터 선택되는 적어도 1종류 이상, 성분 (C) 100 질량부에 대하여 0.05~2.00 질량부가 되는 범위의 양,
(E) 촉매량의 하이드로실릴화 반응용 촉매,
(F) 내열성 부여제
를 함유하는, 경화성 오가노폴리실록산 조성물.(A) 100 parts by mass of an alkenyl group-containing organopolysiloxane having a viscosity of 10 to 100,000 mPa·s at 25°C,
(B) Organohydrogenpolysiloxane: an amount of 0.1 to 10 moles of hydrogen atoms bonded to silicon atoms in component (B) relative to 1 mole of alkenyl groups contained in component (A),
(C) thermally conductive filler, in an amount ranging from 60 to 90% by volume based on the total solid content in the composition,
(D) at least one type selected from fatty acids, fatty acid esters, and fatty acid metal salts, in an amount ranging from 0.05 to 2.00 parts by mass based on 100 parts by mass of component (C),
(E) a catalytic amount of a catalyst for hydrosilylation reaction,
(F) Heat resistance imparting agent
A curable organopolysiloxane composition containing.
(G) 이하의 성분 (G1) 및 성분 (G2)로부터 선택되는 1종류 이상의 성분
(G1) 일반식 (1):
[화 1]
(식 중, R1은 독립적으로 비치환 또는 치환된 탄소-탄소 이중 결합을 갖지 않는 1가 탄화수소기이고, R2는 독립적으로 수소 원자, 알킬기, 알콕시알킬기 또는 아실기이고, a는 5~250의 정수이고, b는 1~3의 정수이다.)로 표시되고, 25℃에서의 점도가 10~10,000 mPa·s 미만인 오가노폴리실록산,
(G2) 일반식 (2):
RalkR3 2SiO(R3 2SiO)cR3 2Si-R4-SiR3 (3-d)(OR5)d
(식 중, Ralk는 알케닐기이고, R3은 독립적으로 비치환 또는 치환된 탄소-탄소 이중 결합을 갖지 않는 1가 탄화수소기이고, R4는 산소 원자 또는 2가 탄화수소기이고, R5는 독립적으로 수소 원자, 알킬기, 알콕시알킬기 또는 아실기이고, c는 1~250의 정수이고, d는 1~3의 정수이다.)로 표시되고, 25℃에서의 점도가 10~10,000 mPa·s의 범위에 있는, 분자쇄 말단에 알케닐기 및 가수 분해성 실릴기를 갖는 실록산계 화합물, 및
(H) 분자 내에 탄소 원자수 6 이상의 알킬기를 갖는 알콕시실란 또는 그의 가수 분해 축합물
로부터 선택되는 1종류 또는 2종류 이상을 포함하는, 경화성 오가노폴리실록산 조성물.According to any one of claims 1 to 4, additionally
(G) One or more components selected from the following components (G1) and (G2)
(G1) General formula (1):
[Tuesday 1]
(In the formula, R 1 is independently an unsubstituted or substituted monovalent hydrocarbon group without a carbon-carbon double bond, R 2 is independently a hydrogen atom, an alkyl group, an alkoxyalkyl group or an acyl group, and a is 5 to 250 is an integer, and b is an integer of 1 to 3. Organopolysiloxane represented by ) and having a viscosity of less than 10 to 10,000 mPa·s at 25°C,
(G2) General formula (2):
R alk R 3 2 SiO(R 3 2 SiO) c R 3 2 Si-R 4 -SiR 3 (3-d) (OR 5 ) d
(Wherein, R alk is an alkenyl group, R 3 is independently an unsubstituted or substituted monovalent hydrocarbon group without a carbon-carbon double bond, R 4 is an oxygen atom or a divalent hydrocarbon group, and R 5 is It is independently a hydrogen atom, an alkyl group, an alkoxyalkyl group, or an acyl group, c is an integer of 1 to 250, and d is an integer of 1 to 3.), and has a viscosity of 10 to 10,000 mPa·s at 25°C. siloxane-based compounds having an alkenyl group and a hydrolyzable silyl group at the molecular chain terminal, and
(H) Alkoxysilane or hydrolytic condensate thereof having an alkyl group with 6 or more carbon atoms in the molecule
A curable organopolysiloxane composition comprising one or two or more types selected from the following.
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| JPH07330927A (en) | 1994-06-14 | 1995-12-19 | Shin Etsu Chem Co Ltd | Composition for insulating heat-radiating sheet and insulating heat-radiating sheet |
| JP2002080816A (en) | 2000-07-20 | 2002-03-22 | Dow Corning Corp | Silicone composition and elecrically conductive silicone adhesive formed from this |
| JP2002088227A (en) | 2000-08-08 | 2002-03-27 | Dow Corning Corp | Silicone composition and conductive cured silicone product |
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| WO2013051600A1 (en) * | 2011-10-04 | 2013-04-11 | 株式会社カネカ | Curable resin composition, tablet of curable resin composition, molded body, semiconductor package, semiconductor component and light emitting diode |
| JP7094960B2 (en) * | 2017-07-24 | 2022-07-04 | ダウ・東レ株式会社 | Multi-component curable heat conductive silicone gel composition, heat conductive member and heat dissipation structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH07330927A (en) | 1994-06-14 | 1995-12-19 | Shin Etsu Chem Co Ltd | Composition for insulating heat-radiating sheet and insulating heat-radiating sheet |
| JP2002080816A (en) | 2000-07-20 | 2002-03-22 | Dow Corning Corp | Silicone composition and elecrically conductive silicone adhesive formed from this |
| JP2002088227A (en) | 2000-08-08 | 2002-03-27 | Dow Corning Corp | Silicone composition and conductive cured silicone product |
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